CN105392776B

CN105392776B - Thio-Salalen catalyst

Info

Publication number: CN105392776B
Application number: CN201480014652.9A
Authority: CN
Inventors: M·科尔; K·普里斯; A·L·斯托佩尔; M.W.赫尔特卡普; M·E·艾万斯; D·A·卡诺
Original assignee: Ramot at Tel Aviv University Ltd; Exxon Chemical Patents Inc
Current assignee: Ramot at Tel Aviv University Ltd; ExxonMobil Chemical Patents Inc
Priority date: 2013-06-20
Filing date: 2014-05-28
Publication date: 2019-02-12
Anticipated expiration: 2034-05-28
Also published as: US20140378634A1; WO2014204624A1; US9150676B2; CN105392776A

Abstract

Catalyst containing thio-salalen ligand.In addition, the catalyst system containing the catalyst and activator；Prepare ligand, the method for catalyst and catalyst system；Use the catalyst and/or catalyst system, the method for olefin polymerization；With the olefin polymer prepared according to this method.

Description

Thio-Salalen catalyst

Related application

This application claims the priority and right for the U.S. Provisional Application 61/837,554 that on June 20th, 2013 submits, It is introduced herein by reference full text.

Invention field

The present invention relates to catalyst compounds and the catalyst system containing this compound, preparation method, user Method and thus obtained product.

Background of invention

Olefin polymerization catalysis industrially has huge purposes.Therefore, effective in the business for finding increase catalyst Property and allow produce have improve performance polymer new catalyst system in be interesting.

There is a need in the art for novel and improved catalyst and catalyst systems, to obtain novel and improved polyolefin, With polymerization etc..Therefore, there is a need in the art for the novel and improved catalyst system for olefin polymerization, in order that one Or multiple following purposes: one or more specific polymer performances, such as high polymer fusing point and/or high polymer point are realized Son amount；Increase the incorporation of conversion ratio or comonomer；And/or changes the distribution of comonomer and do not deteriorate resulting polymers Performance.

Summary of the invention

The disclosure is related to catalyst compounds, the catalyst system containing this compound, the catalyst The preparation method for closing object and system, using the method for this catalyst compounds and polymerization-filling alkene, and has this method to obtain The polyolefin obtained.In an embodiment according to the present invention, catalyst compounds include with metal coordination, sub- by four teeth Two substituted compounds of the 3rd, 4,5 and/or 6 race of bis- (phenates) the ligand system carryings of aminothio, referred to herein as sulphur Generation-salalen ligand system.

The present invention relates to the catalyst compounds indicated with following formula:

Wherein each solid line represents covalent bond and each dotted line represents the coordination journey of modified covalent degree and variation The chemical bond of degree；

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

Wherein every X independently is monovalent C₁-C₂₀Alkyl, the functional group containing the element of 13-17 race in the periodic table of elements, Or in which n is 2, every X can be connected together, form C₄-C₆₂Cyclic annular or polycyclic ring structure；

Wherein Y is selected from divalent C₃-C₂₀Alkyl, containing the divalent functional groups of the element of 13-17 race in the periodic table of elements and its Combination；With

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It independently is hydrogen, C₁-C₄₀Alkyl, the week containing element The functional group of the element of phase Biao 13-17 race or two or more R¹-R¹¹It can connect independently together, form C₄-C₆₂Ring Shape or polycyclic ring structure.

The invention further relates to the catalyst system containing this compound, the preparation method of the catalyst compounds and system, Using the method for this catalyst compounds and polymerization-filling alkene, and the polyolefin obtained by this method.

Brief description

Fig. 1 is embodiment according to the present invention A, the molecular structure-Zr (O-tert- measured by Advances in crystal X-ray diffraction Bu)₂Schematic diagram；

Fig. 2 is embodiment according to the present invention C, the molecular structure-Zr (O-tert- measured by Advances in crystal X-ray diffraction Bu)₂Schematic diagram；With

Fig. 3 is embodiment according to the present invention G, the molecular structure-Zr (O-tert- measured by Advances in crystal X-ray diffraction Bu)₂Schematic diagram.

It is described in detail

For the purpose of the present invention and claim, the period in Chem.Eng.News, 1985,63,27 is used The new numbering plan of table race.Therefore, " group-4 metal " is the element of the 4th race in periodic table, such as Hf, Ti or Zr.

In the structure described in specification and claims, solid line indicates that chemical bond, arrow indicate the chemical bond Can be coordinate bond and each dotted line indicates the chemical bond of modified covalent degree and the coordination degree changed.

Term " hydrocarbyl residue ", " alkyl " and " hydrocarbyl group " are used interchangeably in the literature, unless otherwise indicated. For the purpose of the disclosure of invention, alkyl is defined as C₁-C₇₀Residue or C₁-C₂₀Residue or C₁-C₁₀Residue, or C₆-C₇₀Residue or C₆-C₂₀Residue or C₇-C₂₀Residue, they can be straight chain, straight chain or ring-type, and optionally (aromatics is non- Aromatics)；And including by other alkyl and/or one or more of functional groups containing the element of 13-17 race in the periodic table of elements Substituted alkyl.In addition, two or more such alkyl can be formed together fused ring system, including partly or completely perhydro The fused ring system of change, the fused ring system may include heterocycle.

Term " substitution " refer to hydrogen atom in basic structure and/or carbon atom by alkyl and/or functional group, And/or hetero atom or containing heteroatomic group replace.Therefore, term alkyl includes containing heteroatomic group.For the mesh of this paper For, hetero atom is defined as any atom in addition to carbon and hydrogen.For example, methyl cyclopentadiene (Cp) is replaced by methyl Cp base (it is basic structure), it is alternatively referred to as methyl functional group, and ethyl alcohol is that (it is base by ethyl that-OH functional group replaces This structure) and pyridine be the phenyl that the carbon in the basic structure of phenyl ring is replaced by nitrogen-atoms.

For the purpose of this paper, alkyl can be independently selected from substituted or unsubstituted methyl, ethyl, vinyl, And the isomers of following radicals: propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecane Base, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, two Undecyl, docosyl, eicosyl, tricosyl, tetracosyl, pentacosyl, cerul, 20 Seven alkyl, octacosyl, nonacosyl, melissyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octene Base, nonenyl, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, pentadecane alkenyl, 16 Carbene base, heptadecene base, octadecene base, 19 carbene bases, eicosylene base, heneicosene base, two dodecenyl succinics, Tricosene base, tetracosa carbon alkenyl, ppentacosene base, cerotene base, cerotene base, two octadecenes Base, 29 carbene bases, melene base, propinyl, butynyl, pentynyl, hexin base, heptynyl, octynyl, n-heptylacetylene base, Decynyl, hendecyne base, dodecyne base, 13 carbyne bases, 14 carbyne bases, pentadecane alkynyl, hexadecine base, 17 Carbyne base, octadecyne base, 19 carbyne bases, 20 carbyne bases, two hendecyne bases, two dodecyne bases, 23 carbynes Base, tetracosa carbon alkynyl, two pentadecane alkynyls, two hexadecine bases, 27 carbyne bases, two octadecyne bases, 29 carbon Alkynyl and 30 carbyne bases.

For the purpose of this paper, alkyl may also comprise saturation, partially unsaturated and aromatic cyclic structure isomers, Wherein the group can be additionally carried out the substitution of types described above.Term " aryl ", " aromatic yl residue " and/or " aryl group " are Refer to aromatic cyclic structure, it can be replaced by alkyl defined herein and/or functional group.The example of aryl includes acenaphthenyl, acenaphthylene Base, acridinyl, anthryl, benzo anthryl, benzimidazolyl, benzo isoxazolyl, benzofluoranthrene base, benzofuranyl, benzo two Rylene base, benzo pyrenyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzyl, carbazyl, carboline base, 1,2- benzene And phenanthryl, cinnoline base, coronene base, cyclohexyl, cyclohexenyl group, methylcyclohexyl, dibenzo anthryl, fluoranthene base, fluorenyl, Furyl, imidazole radicals, indazolyl, indeno pyrenyl, indyl, indolinyl, isobenzofuran-base, isoindolyl, isoquinolin Base, isoxazolyl, methylbenzyl, aminomethyl phenyl, naphthalene, oxazolyl, phenanthryl, phenyl, purine radicals, pyrazinyl, pyrazolyl, pyrene Base, pyridazinyl, pyridyl group, pyrimidine radicals, pyrrole radicals, quinazolyl, quinolonyl, quinoxalinyl, thiazolyl, thienyl and similar Group.

It is appreciated that, when listing a group, it indicates the basic structure (base of the group for the purpose of this paper Group's type) and carry out the every other group formed when above-described substitution to the group.Cited alkyl, alkenyl and Alkynyl includes all isomers, and including cyclic isomers optionally, such as butyl includes normal-butyl, 2- methyl-propyl, 1- methyl-propyl, tert-butyl and cyclobutyl (and cyclopropyl of analog substitution)；Amyl includes n-pentyl, cyclopenta, 1- methyl Butyl, 2- methyl butyl, 3- methyl butyl, 1- ethyl propyl and neopentyl (and cyclobutyl and cyclopropyl of analog substitution)； Cyclobutenyl includes 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- methyl-1-propylene base, 1- methyl -2- acrylic, 2- methyl - The E and Z-shaped formula of 1- acrylic and 2- methyl -2- acrylic (and cyclobutane base and cyclopentenyl).Ring-typeization with substituent group Closing object includes all isomeric forms, such as aminomethyl phenyl will include ortho-methyl phenyl, m- aminomethyl phenyl and p- methylbenzene Base；3,5-dimethylphenyl will include 2,3- 3,5-dimethylphenyl, 2,4- 3,5-dimethylphenyls, 2,5- 3,5-dimethylphenyls, 2,6- diphenylmethyls Base, 3,4- 3,5-dimethylphenyls and 3,5- 3,5-dimethylphenyl.

Equally, term " functional group ", " group " and " substituent group " can also be used interchangeably in the literature, unless otherwise saying It is bright.For the purpose of this paper, functional group includes having containing the element of the 13rd, 14,15,16,17 race in the periodic table of elements Both machine and inorganic group and part.Suitable functional group may include alkyl, such as alkyl, alkenyl, aryl and/or halogen (Cl, Br, I, F), O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR *_x, PbR*_xAnd/or analog, wherein R* is C defined above₁-C₂₀Alkyl, and wherein x is suitable integer, to provide electricity Neutral fraction.Other examples of functional group include being typically called amine, acid imide, amide, ether, alcohol (hydroxyl (hydroxides)), sulfenyl, sulfuric ester (salt), phosphorus base, halogen, phosphonate ester (salt), alkoxide, ester, carboxylate (salt), aldehyde Those of with analog.

For the purpose of this paper, " direct chemical bond ", " direct covalent bond " or " direct bridging " is interchangeable It uses, refers to the covalent bond directly between the atom for not having any insertion atom.

For the purpose of this paper, " alkene ", or being known as " olefine " is to contain carbon at least one double bond With the straight chain of hydrogen, branch or cyclic compound.For the purpose of this specification and appended claims, when polymer or When copolymer is known as olefin-containing, existing alkene is the polymerized form of the alkene in this polymer or copolymer.For example, working as When mentioning copolymer has " ethylene " content of 35wt%-55wt%, it is understood that derivative for the monomeric unit in the copolymer Ethylene and the derivative unit in polymerization reaction exist with 35wt%-55wt%, the weight based on the copolymer.

For the purpose of this paper, " polymer " there are two or more identical or different " monomer " units." Polymers " is the polymer with same monomer unit." copolymer " is that have two or more monomeric units different from each other Polymer." terpolymer " is the polymer with three monomeric units different from each other.It mentions in monomeric unit " no Refer to that monomeric unit differs at least one atom each other or monomeric unit isomery is different together ".Therefore, used herein total The definition of polymers includes terpolymer and analog.Oligomer typically has low molecular weight, such as Mn less than 25, 000g/mol, or in an embodiment according to the present invention, less than 2,500g/mol or the monomer list of low quantity Member, the polymer of e.g., less than or equal to 75 monomeric units." ethene polymers " or " ethylene copolymer " is containing at least The polymer or copolymer of the unit of 50mol% ethylene derivative, " acrylic polymers " or " propylene copolymer " are containing at least The polymer or copolymer of the unit of 50mol% propylene derived, so analogize.

For the purpose of the disclosure of invention, term " alpha-olefin " includes C₂-C₂₂Alkene.Alpha-olefin it is unrestricted Property example includes ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- nonene, 1- decene, 11 carbon of 1- Alkene, 1- dodecylene, 1- tridecylene, tetradecene, 1- pentadecane alkene, cetene, 1- heptadecene, 18 carbon of 1- Alkene, 19 carbene of 1-, 1- eicosylene, 1- heneicosene, bis- dodecylene of 1-, 1- tricosene, 1- tetracosene, 1- ppentacosene, 1- cerotene, 1- cerotene, bis- octadecene of 1-, 29 carbene of 1-, 1- melene, 4-methyl-1-pentene, 3- Methyl-1-pentene, 5- methyl-1-nonene, 3,5,5- trimethyl-1- hexenes, vinyl cyclohexane, and Vinyl norbornene alkane.The non-limiting example of cyclic olefin and alkadienes includes cyclopropylene, cyclobutane, cyclopentene, cyclohexene, Cycloheptene, cyclo-octene, cyclonoene, cyclodecene, norbornene, 4- methyinorbornene, 2- methyl cyclopentene, 4- methyl ring penta Alkene, vinyl cyclohexane, norbornadiene, bicyclopentadiene, 5- ethylidene -2- norbornene, vinylcyclohexene, 5- ethylene Base -2- norbornene, 1,3- divinyl pentamethylene, 1,2- divinylcyclohexane, 1,3- divinylcyclohexane, Isosorbide-5-Nitrae-two Vinyl cyclohexane, 1,5- divinyl cyclooctane, 1- allyl -4- vinyl cyclohexane, Isosorbide-5-Nitrae-diallyl hexamethylene, 1- Allyl -5- vinylcyclooctane and 1,5- diallyl cyclooctane.

Term " catalyst ", " catalyst compounds " and " transistion metal compound " are defined as referring in suitable condition Under, the compound of polymerization catalyzed effect can be caused.In the description herein, catalyst can be described as catalyst precarsor, Before-catalyst compounds or transistion metal compound and these terms are used interchangeably.Catalyst compounds can be independent Using causing catalytic action, or catalytic action can be caused with activator combination use.When catalyst compounds quilt With activator combination come when causing catalytic action, which is commonly referred to as procatalyst or catalyst precarsor.It " urges Agent system " is at least one catalyst compounds, at least one activator, optional activator promotor and optional carrier material Combination, wherein the system polymerisable monomer is at polymer.For the purpose of the present invention and claim, work as caltalyst When system is described as including the neutral stable form of component, those skilled in the art be will be best understood, the ion shape of the component Formula is that the form of polymer is generated with monomer reaction.

For the purpose of this paper, term " productivity (catalyst productivity) of catalyst " is small in T When period in, use catalyst containing Wg (cat) polymerization catalyst produce how many grams of polymer (P) measurement；And it can It is expressed by following the equation: P/ (T x W) and with unit gPgcat^-1hr^-1Expression.Conversion ratio is to be converted to polymeric articles Amount of monomer, and reported with mol%, and calculated based on polymer yield and the amount of monomer being fed in reactor.Catalyst Activity is catalytic activity measurement how and the product polymer (P) for being reported as used every mol catalyst (cat) production Quality (kg P/mol cat).

" anion ligand " is the ligand that the bear electricity of one or more pairs of electronics is supplied to metal ion." neutral donor is matched Body " is the ligand that the electroneutral of one or more pairs of electronics is supplied to metal ion.

Scavenger is the compound for promoting polymerization reaction to be typically added by removing impurity.Some scavengers can also fill When activator and it can be described as activator promotor.The activator promotor of non-scavenger can also be used in combination with activator, to form activity Catalyst.In an embodiment according to the present invention, activator promotor can be premixed with catalyst compounds, be formed alkylated Catalyst compounds.

Mn used herein be by proton magnetic resonance (PMR) chromatography (¹H NMR) measurement number-average molecular weight, unless It is otherwise noted, Mw, which is by the weight average molecular weight and Mz of gel permeation chromatography (GPC) measurement, to be divided equally by the z of GPC measurement Son amount, wt% is weight percent and mol% is molar percentage.Molecular weight distribution (MWD) is defined as Mw divided by Mn.It removes Non- to be otherwise noted, the unit of all molecular weight, such as Mw, Mn, Mz are reported with g/mol.

Following abbreviations can be used in this specification: Me is methyl, and Ph is phenyl, and Et is ethyl, and Pr is propyl, iPr It is isopropyl, n-Pr is n-propyl, and Bu is butyl, and iso- butyl is isobutyl group, and sec- butyl refers to sec-butyl, tert- butyl, T- butyl, tert-Bu or t-Bu refer to that tert-butyl, n- butyl are normal-butyls, and pMe is p- methyl, and Bz is benzyl, and THF is four Hydrogen furans, Mes are mesitylene base, also referred to as 1, and 3,5- trimethylbenzenes, Tol is toluene, and TMS is trimethyl silyl, TIBAL is triisobutyl aluminium, and TNOAL is triisobutyl octyl aluminum, and MAO is methylaluminoxane and MOMO is methoxyl group methoxy Base (also referred to as methoxy ether).Trityl-D4 is triphenylcarbenium four (pentafluorophenyl group) borate, and N is nitrogen and O is oxygen (including O^a, O^b, O¹, O²It is oxygen).

For the purpose of this paper, composition before transitional phrase " containing ", element or one group of element it is any when Wait, it is understood that we also consider in citation the composition, before one or more elements have transitional phrase " substantially by ... Composition ", " Consists of ", the same combination of " being selected from ... " or "Yes" or one group of element, and vice versa.

For the purpose of this paper, RT is room temperature, it is defined as 25 DEG C, unless otherwise indicated.All percentages are Weight percent (wt%), unless otherwise indicated.

In the present specification, thio-salalen catalyst can be described as catalyst precarsor, procatalyst compound, sulphur Generation-salalen catalyst compounds or transistion metal compound and these terms are used interchangeably.

Pass through¹³C-NMR spectroscopic methodology measures polyacrylic micro-structure, including isotaxy and syndiotaxy Unit two Group ([m] and [r]), the concentration of three unit groups ([mm] and [rr]) and five unit groups ([mmmm] and [rrrr]).Symbol " m " Or " r " describes the spatial chemistry of adjacent acrylic pair, " m " refers to that meso and " r " refer to racemic.It dissolves a sample in d₂In -1,1,2,2- tetrachloroethanes, and use 100MHz (or higher) NMR spectrometer, the recording light spectrogram at 125 DEG C.It mentions Formant to polymer is mmmm=21.8ppm.It is described in characterizing the calculating involved in polymer by NMR The Polymer Conformation and Configuration (Academic Press, New York 1969) of F.A.Bovey and J.Randall Polymer Sequence Determination, 13C-NMR Method (Academic Press, New York, 1977) in.

Using differential scanning calorimetry (DSC), on commercially available instrument (such as TA Instruments 2920DSC) Measure the fusing point (Tm or T melting) of polymer, also referred to as melting temperature and melting enthalpy (Hf).Typically, 6- is sealed in aluminium dish The polymer of 10mg molding or the polymer of plasticizing, and be loaded in instrument at room temperature.Pass through the heating speed in 10 DEG C/min Under rate, heating sample is at least 30 DEG C higher than its melting temperature, for polypropylene, 220 DEG C, obtains and melts data (heating for the first time).It is kept for sample at least 5 minutes at this temperature, destroys its thermal history.Pass through the cooling in 20 DEG C/min Under rate, from the cooling sample of molten condition at least 50 DEG C lower than crystallization temperature, for polypropylene, -50 DEG C, obtain Obtain crystal data.It is kept for sample at least 5 minutes, and is finally heated at 10 DEG C/min at this temperature, obtain additional melt Melt data (second of heating).According to standard procedure, analysis heat absorption melting transition (being heated for the first time with second) and heat release knot Crystalline substance transformation.The melting temperature reported is the peak melt temperature from second of heating, unless otherwise prescribed.

For the polymer for showing multiple peaks, melting temperature be defined as from the thermal response of maximum caloric receptivity (without It is at the peak that maximum temperature occurs) the peak value melt temperature of relevant fusion curve.Area under DSC curve, which is used to determine, to be turned Heating (the hot H of fusing when melting_f), it can be used to calculate crystallinity (also referred to as crystallinity %).It is calculated and is tied using following formula Brilliant degree % (X%): [area under a curve (being indicated with J/g)/H ° (being indicated with J/g)] * 100, wherein H ° is major monomeric compoent Homopolymer perfect crystallization ideal fusing it is hot.These H ° numerical value be obtained from Polymer Handbook, fourth edition, by John Wiley and Sons is published, and New York 1999, difference is, the numerical value of 290J/g is used for H ° (polyethylene), 140J/g's Numerical value is used for H ° (polypropylene) for the numerical value of H ° (polybutene) and 207J/g.

For the purpose of this paper, each solid line of chemical structure represents covalent bond and each dotted line represents to have and become The chemical bond of the coordination degree of the covalent degree and variation changed.

It is huge on imino group thiobis (phenates) or thio salalen catalyst compounds for the purpose of this paper Big ligand substituting base is defined as C₄-C₂₀Alkyl；--SR^a, -- NR^a ₂With -- PR^a ₂, wherein every R^aIt independently is C₄-C_{20 hydrocarbon}Base； Or C₄-C₂₀The organic quasi-metal that alkyl replaces.The molecular volume of the substituent group used herein approximation huge as space multistory. Permission is compared compared with the substituent group with bigger molecule volume to the substituent group with different molecular volume, is had compared with small molecule The substituent group of volume is considered as " less huge ".On the contrary, there is larger point compared with there is the substituent group compared with small molecule volume The substituent group of sub-volume can be considered as " huger ".

It can be such as " A Simple ' Back of the Envelope ' Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,”Journal of Chemical Education, volume 71, o. 11th is reported in the 962-964 pages, calculates molecular volume in November in 1994.Use following formula: MV =8.3Vs is calculated molecular volume (MV), cubic unitWherein Vs is conversion (scaled) volume.V is the phase of constituting atom To the sum of volume, and using the relative volume of following table, calculated according to the molecular formula of substituent group.For condensed ring, for each Condensed ring, Vs decline 7.5%.

For the purpose of this paper, huge substituent group is defined as molecular volume more than or equal to tert-butyl substituent Any substituent group (MV=8.3Vs=141.1).The example of other suitable huge substituent groups includes adamantyl, and halogen takes Generation and unsubstituted aromatic functional groups, and similar group.

For the purpose of this paper, the thio-salalen catalyst compounds of bridging refer to four teeth with metal coordination Imino group thiobis (phenates) ligand system.Thio-salalen ligand system includes [O^a,N,S,O^b], wherein O^aIt is connected to N On the first half of the ligand containing imines-phenoxide moieties and S and O^bIt is connected to the second half of the ligand containing thio phenoxide moieties On.The first the half of the ligand and the second half are connected on each other by the bridge portion Y between N and S.Every O^a, N, S and O^b? It is bonded on metallic atom in hexa-coordinate arrangement.For the purpose of this paper, the thio-salalen catalyst compounds of bridging Object has one of general formula structure I or II:

Wherein R¹-R¹¹, M, n, X, X¹, X²It is as described below with Y.

For the purpose of this paper, " fac " (face (facial)) structure refers to thio-salalen ligand structure II, Wherein in the hexa-coordinate arrangement centered on metallic atom, O^aAnd/or O^bNot in [N, S, M] plane, or different earth's surfaces It states, all three atoms [O^a, N, S] and/or and/or all three atoms [N, S, O^b] ([O in same side^a, S] and [N, O^b] positioned at cis-)；And in " mer " (meridian plane (meridional)) structure, O^aAnd/or O^bIn [N, S, M] plane, or It differently states, relative to S, O^a(it is located at trans-) on the opposite side of the heart in a metal, and/or for N, O^bThe heart in a metal On opposite side.For the purpose of this paper, in binary package (wrapping) mode name, structure [O is addressed first^a,N, S] and the second [N, S, O^b] such as " fac-mer " refer to fac [O^a, N, S] and mer [N, S, O^b]。

O^a-N-S-O^bThe possible arrangement of four kinds of thio-salalen catalyst compounds is: mer-mer, in the art Relative to reactive group X¹And X², also referred to as trans-；Fac-fac, in the art also referred to as cis--α；And fac-mer and Mer-fac, generally referred to as cis--β, but it is actually different isomers as described below.

Catalyst compounds

In an embodiment according to the present invention, catalyst includes being matched by the four thio-salalen of two-anion of tooth The dialkyl compound of 3rd, 4,5 and/or 6 race of body carrying.In some embodiments of the present invention, which can be used for Olefin polymerization and/or alpha-olefin, to produce polyolefin and/or poly- (alpha-olefin).

In an embodiment according to the present invention, catalyst compounds are indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein every X¹And X²It independently is monovalent C₁-C₂₀Alkyl, the official containing the element of 13-17 race in the periodic table of elements It can group or X¹And X²It connects together, forms C₄-C₆₂Cyclic annular or polycyclic ring structure；

Some embodiments according to the present invention, catalyst include the [O of fac-mer, mer-fac or fac-fac arrangement¹, N,S]-[N,S,O²]。

A special embodiment according to the present invention, M are Hf or Zr.In some embodiments, X¹And X²Respectively Benzyl.In embodiments of the invention, X¹And X²Respectively halogen.

In an embodiment according to the present invention, every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It is independent Ground is hydrogen, halogen or C₁-C₃₀Alkyl.

In an embodiment according to the present invention, every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It is independent Ground is hydrogen, halogen or C₁-C₁₀Alkyl.

According to a special embodiment, Y includes o- phenylene bivalent group.

A special embodiment according to the present invention, catalyst compounds are indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

According to a special embodiment, catalyst compounds are indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein every X¹And X²It independently is monovalent C₁-C₂₀Alkyl, the official containing the element of 13-17 race in the periodic table of elements It can group or X¹And X²It connects together, forms C₄-C₆₂Cyclic annular or polycyclic ring structure；With

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴And R¹⁵It independently is hydrogen, C₁-C₄₀ Alkyl, the functional group of the element of the race containing periodic table of elements 13-17 or two or more R¹-R¹⁵It can connect independently together It connects, forms C₄-C₆₂Cyclic annular or polycyclic ring structure.

In an embodiment according to the present invention, catalyst compounds include fac-mer, mer-fac or fac-fac [the O of arrangement¹,N,S]-[N,S,O²].In an embodiment according to the present invention, catalyst compounds include fac-fac row [the O of column¹,N,S]-[N,S,O²]。

In of the invention one special embodiment, X¹And X²It is benzyl；At least one R², R⁴, R⁵And R⁷Independently It is selected from: C₁-C₁₀Alkyl, C₁-C₁₀Naphthenic base, C₁-C₁₀Alkenyl C₁-C₁₀Alkoxy, the C that aryl replaces₁-C₁₀Alkyl, C₁-C₁₀Virtue Base, halogen group and combinations thereof；And R¹, R³, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴And R¹⁵It is hydrogen.

In of the invention one special embodiment, at least one R², R⁴, R⁵And R⁷Independently selected from: methyl, second Base, isopropyl, isobutyl group, tert-butyl, isopentyl, 2- methyl -2- phenylethyl；Methoxyl group, benzyl, adamantyl, chlorine, bromine, Iodine and combinations thereof.

In of the invention one special embodiment, R⁴, R⁵Or combinations thereof be chlorine, bromine, iodine, huge ligand substituting Base, or combinations thereof, huge ligand substituting base includes the molecular volume that molecular volume is greater than or equal to tert-butyl substituent；And Pang Big ligand substituting base includes C₄-C₂₀Alkyl, -- SR^a, -- NR^a ₂, -- PR^a ₂Or combinations thereof, wherein R^aIt independently is C₄-C₂₀Hydrocarbon Base.

In of the invention one special embodiment, R⁴It is containing C₄-C₂₀The huge ligand substituting base and R of alkyl^{5 are} Chlorine, bromine or iodine.

In an embodiment according to the present invention, catalyst system includes:

Activator and the catalyst compounds indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

According to a special embodiment, [O¹,N,S]-[N,S,O²] it is that fac-mer, mer-fac or fac-fac are arranged Column.In an embodiment according to the present invention, [O¹,N,S]-[N,S,O²] it is that fac-fac is arranged.

In an embodiment according to the present invention, activator includes aikyiaiurnirsoxan beta, the anion active agent of non-coordination or A combination thereof.In a special embodiment, activator includes aikyiaiurnirsoxan beta and aikyiaiurnirsoxan beta to be greater than or equal to 1mol aluminium/mol The ratio of catalyst compounds exists.

In of the invention one special embodiment, activator is indicated with following formula:

(Z)_d ⁺(A^d-)

Wherein Z is (L-H) or reducible lewis acid, and wherein L is neutral Lewis base, and H is hydrogen and (L-H)⁺It is cloth Lanace platform moral acid；

A^d-It is with charge d^-Non- coordination anion^-；With

D is the integer of 1-3.

In an embodiment according to the present invention, activator is indicated with following formula:

(Z)_d ⁺(A^d-)

Wherein A^d-It is with charge d^-Non- coordination anion；

D is the integer of 1-3, and

Z is with following formula: (Ar₃C⁺) indicate reducible lewis acid, wherein Ar is aryl, the virtue being exchanged for heteroatoms Base, by one or more C₁-C₄₀The aryl that alkyl replaces, by the one of one or more element containing periodic table of elements 13-17 race The aryl that a or multiple functional groups replace, or combinations thereof.

In an embodiment according to the present invention, there are two or more in catalyst system used herein The different catalyst compounds of kind.In an embodiment according to the present invention, there are two or more in reaction zone Different catalyst compounds, wherein technique described herein occurs in the reaction zone.It is used when in a reactor When two kinds of transistion metal compound base catalyst are as hybrid catalyst system, two kinds of transistion metal compounds are preferably selected, are made It is preferably compatible to obtain the two.Compatible catalyst is that have to terminate dynamics similar with comonomer with insertion monomer and/or do not have Have deleteriously with interact with each other those of catalyst.For the purpose of this paper, term " incompatible catalyst " is Refer to and mean to meet one or more following catalyst:

1) in the presence of together, at least one catalyst activity is reduced more than those of 50% catalyst；

2) under identical reactive conditions, polymer produced makes the molecular weight of one of polymer than other polymerizations Those of big twice of molecular weight catalyst of object；With

3) under the same conditions, the incorporation of comonomer or reactivity differ by more than about those of 30% catalyst.It can make With a kind of simple screening technique, such as by well known by persons skilled in the art¹H or¹³C NMR, which kind of transition gold measured It is compatible for belonging to compound.In an embodiment according to the present invention, catalyst system, which uses, is directed to catalyst compounds Identical activator.In an embodiment according to the present invention, it may be used in combination two or more different activators, Such as non-coordinating anion activator and aikyiaiurnirsoxan beta.If one or more catalyst compounds contain non-hydride ion or alkyl X¹Or X²Ligand, then in an embodiment according to the present invention, before adding non-coordinating anion activator, contact Aikyiaiurnirsoxan beta and catalyst compounds.

It, can when using two kinds of transistion metal compound (procatalysts) in an embodiment according to the present invention Use two kinds of transistion metal compounds of any ratio.In an embodiment according to the present invention, First Transition metallization 1:1000 to 1000:1 or 1:100 will be fallen in 500 to the molar ratio (A:B) of Second Transition compound (B) by closing object (A): In the range of 1 or 1:10 to 200:1 or 1:1 to 100:1 or 1:1 to 75:1 or 5:1 to 50:1.Selected special ratios will Depending on selected exact procatalyst, activation method and required final product.In an embodiment party according to the present invention In case, when using two kinds of procatalysts, in the case where the two is activated with identical activator, always rubbing based on procatalyst You, useful mol% is 10:90 to 0.1:99 or 25:75 to 99:1 or 50:50 to 99.5:0.5 or 50:50 to 99:1, Or 75:25 to 99:1 or 90:10 to 99:1.

The method for preparing catalyst compounds

In an embodiment according to the present invention, by making amineothiot (NH₂- Y-SH, wherein Y as above determines Justice), halogenated-methylphenol and bigcatkin willow aldehyde reaction form thio-salalen ligand, thus before preparing thio-salalen ligand Body.In some embodiments, amineothiot (NH₂- Y-SH) reacted with halogenated-methylphenol, formed amino-it is thio-methyl Phenol and amino-it is thio-methylphenol itself again reacted with bigcatkin willow.In other embodiments, amineothiot (NH₂-Y-SH) With bigcatkin willow aldehyde reaction, forms thio imino group phenol and thio imino group phenol itself and reacted with halogenated-methylphenol.

In an embodiment according to the present invention, the phenol in conjunction with amino-mercaptan and halogenated methyl substitution can be passed through Between nucleophilic displacement of fluorine and imines-condensation reaction, prepare thio-salalen ligand, if using be located at hydroxy functional group ortho position Aldehyde (such as substituted salicylide foundation structure) if.In an embodiment according to the present invention, usually following anti- Answer the substituent group on the phenyl ring indicated in formula A-E with R and R ' can be identical, to generate the symmetrical sulphur for replacing (relative to phenol ring) Generation-salalen ligand, or can be different, to generate the thio-salalen ligand of Asymmetrical substitute (relative to phenol ring). R ' substituent group corresponds to the R in the thio-salalen of above formula¹, R², R³, R⁴And R¹¹And R substituent corresponds to R⁵, R⁶, R⁷, R⁸, R⁹ And R¹⁰。

In an embodiment according to the present invention, 2- (halogenated methyl) R fortified phenol, such as 2- amineothiot phenol It can be with amineothiot (NH₂- Y-SH) reaction, production amino-is thio-phenol (reaction A, X=halogen) that replaces of methyl R-, it connects Make amino-it is thio-methyl the R- phenol and R ' substituted bigcatkin willow aldehyde reaction that replace, produce (the reaction of thio-salalen ligand B)。

In an embodiment according to the present invention, in amineothiot (NH₂- Y-SH) and the substituted salicylide of R ' between Imines-condensation reaction to produce the substituted phenol of mercaptan imino group R ' (reaction C), can then carry out mercaptan imino group R ' substitution Phenol and 2- (halogenated methyl) the R phenol replaced react, to produce thio-salalen ligand (reaction D).

Then, by being reacted with the also referred to as substituted metal compound of " metalating agent ", by thio-salalen ligand (or Person symmetrically replaces or Asymmetrical substitute) it is converted to the catalyst precarsor of metal di-substituted, obtain final complex compound.In root According in one embodiment of the invention, pass through the metalating agent MX replaced with three-or four-_(n+2)Reaction, by thio-salalen Ligand transformations are at metal labile ligand (X) catalyst precarsor, and wherein n is 1 or 2, (anti-to obtain final transistion metal compound Answer E1), or the metalating agent MX by replacing with four-₄Reaction, is converted to two-labile ligand of metal (X) catalyst precarsor, To obtain final transistion metal compound (reaction E2).

React A:

React B:

React C:

React D:

React E1:

React E2:

In some embodiments according to the present invention, it can be contacted in reaction E1 or in reaction E2 with activator Before, thio-salalen ligand and metalating agent are contacted, catalyst compounds are formed, and then can be with or without separation precursor In the case where catalyst compounds, contact catalyst compounds and activator, or can in reaction E1 or in reaction E2, In the presence of catalyst, in the presence of one or more alkene, or a combination thereof under, such as metallize, activate and/or gather in situ It closes in technique, contacts thio-salalen ligand and metalating agent.

Activator

Term " co-catalyst " and " activator " are used interchangeably, to describe activator, and be defined as can by will in Property catalyst compounds be converted to catalytic activity catalyst compounds cation, urged to activate above-described any one Any compound of agent compound.Unrestricted activator ionizes activator (they for example including aikyiaiurnirsoxan beta, alkyl aluminum Can be neutral or ion), and the co-catalyst of routine-type.Activator may include aluminium alkoxide compound, modified alumoxane Compound, and ionization anion pre-cursor compounds, σ-bonding gold of the ionization anion pre-cursor compounds abstraction reaction Metal ligand so that metal complex is at cation, and provides that charge-balance is noncoordinating or the anion of weak coordination.

In one embodiment of the invention, alumoxane activator is used as activator in carbon monoxide-olefin polymeric.Alumina Alkane is usually containing-Al (R¹)-O- subelement oligomeric compound, wherein R¹It is alkyl.The example of aikyiaiurnirsoxan beta includes methyl alumina Alkane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutyl aluminium alkoxide.Alkylaluminoxane and modified alkyl aluminium Oxygen alkane is suitable as catalyst activator, especially when the catalyst precursor compounds include can abstractable ligand (it is alkyl, halogen Base, alkoxy or amide) when.The mixture of different aluminum modified aluminoxanes can also be used.At one according to the present invention In embodiment, the methylaluminoxane of visually clear can be used.It may filter that muddy or gelling aikyiaiurnirsoxan beta, produce limpid molten Liquid, or limpid aikyiaiurnirsoxan beta can be decanted from muddy solution.Useful aikyiaiurnirsoxan beta is in United States Patent (USP) No.5,041,584 The methylaluminoxane (MMAO) of the modification of description and/or Akzo is available commercially from trade names 3A type modified methylaluminoxane The methylaluminoxane (MMAO) of the modification of Chemicals.

It is living in an embodiment according to the present invention when the activator is aikyiaiurnirsoxan beta (modified or unmodified) The maximum of agent is typically about the M (each metal catalytic site) on 5000 times of molar excess Al/ catalyst compounds. In an embodiment according to the present invention, according to the determining p- catalysis of minimum activator-of the molar concentration of transition metal M Immunomodulator compounds are typically about 1 moles, of aluminum per mole of titanium metal or lower to 1 mol of transition-metal M.In an embodiment according to the present invention, The activator includes aikyiaiurnirsoxan beta, and the aikyiaiurnirsoxan beta exists with ratio of 1 moles, of aluminum per mole of titanium metal or more to 1 mole catalyst immunomodulator compounds.? In an embodiment according to the present invention, the molar ratio of the minimum p- catalyst compounds of activator-is usually 1: 1 molar ratio. Other embodiments of Al: M range include 1: 1 to 500: 1 or 1: 1 to 200: 1 or 1: 1 to 100: 1 or 1: 1 to 50: 1.

In an embodiment according to the present invention, uses few in the polymerization or do not use herein Aikyiaiurnirsoxan beta (i.e. less than 0.001 weight %).In an embodiment according to the present invention, aikyiaiurnirsoxan beta is deposited with 0.00 mole of % Or the aikyiaiurnirsoxan beta with the aluminium less than 500: 1 or less than 300: 1 or less than 100: 1 or less than 1: 1 to catalyst compounds The molar ratio of transition metal exists.

Term " non-coordinating anion " (NCA) refers to not coordinating to cation, or only weak coordinating on cation Thus anion is kept enough vivaciously to be replaced by neutral Lewis base." compatible " non-coordinating anion is to work as to be initially formed Complex compound decompose when be not degraded to those of neutrality.Further, anion will not shift anion substituent or segment To cation to make its formation neutral transition metal compound and from the neutral by-product of anion.According to the present invention may be used Non-coordinating anion is and polymerize or catalyst system is compatible, makes transition-metal cation by balancing its ionic charge + 1 and stabilize, and it is still active enough so that those of being replaced during polymerization.

In an embodiment according to the present invention, the activator of ionization or stoichiometry can be used, can be It is neutral or ionization, for example, three (normal-butyl) ammonium boron metalloid precursors, polyhalo miscellaneous borine (heteroborane) anion (WO 98/43983), boric acid (U.S. Patent number 5,942,459) or their combination.In an embodiment according to the present invention In, neutral or ion activation agent can be used in combination with individually or with the alumoxane activator of aikyiaiurnirsoxan beta or modification.

The example of the activator of neutral stoichiometric includes trisubstituted boron, tellurium, aluminium, gallium and indium or their mixing Object.Three substituent groups or group can be identical or different, and in an embodiment according to the present invention, each independently Selected from substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, alkoxy and halogen.Implement at one according to the present invention In scheme, three groups are independently selected from halogen, single or multiple cyclic annular (replacing including halogen) aryl, alkyl and alkenyl chemical combination Object and their mixture；Or independently selected from the alkenyl with 1-20 carbon atom, the alkyl with 1-20 carbon atom, Alkoxy with 1-20 carbon atom and aryl or substituted aryl with 3-20 carbon atom.At one according to the present invention In embodiment, three substituent groups are the alkyl with 1-20 carbon atom, phenyl, naphthalene or their mixture.In basis In one embodiment of the invention, three groups are halogenated aryl, for example, fluoro aryl.In a reality according to the present invention It applies in scheme, the activator of neutral stoichiometric is three-perfluorophenyl boron or three-perfluoronapthyl boron.

In an embodiment according to the present invention, the activator compound of Ionic stoichiometric may include active matter Son or some other cations, the residual ion association of they and ionic compound, but be not coordinated, or be only loosely Coordination.Suitable example includes the compound etc. for being described in following documents: 0 570 982 A of European Published EP；EP 0 520 732 A；EP 0 495 375 A；EP 0 500 944 B1；EP 0 277 003 A；EP 0 277 004 A；U.S. patent Nos.5,153,157；5,198,401；5,066,741；5,206,197；5,241,025；5,384,299；5,502,124；With WO 1996/04319；All documents are introduced by reference.

In an embodiment according to the present invention, the compound as activator includes that (cation is cation Such as the Bronsted acid of proton can be provided) and relatively large (huge) compatible non-coordinating anion, the anion The active catalyst species (for example, the 4th race is cationic) formed when two kinds of compounds combine, and the yin can be stablized Ion will be enough vivaciously to be replaced by olefinic, diolefins or acetylene series unsaturated materials or other neutral Lewis bases such as ether, amine etc. It changes.The available compatible non-coordinating anion of two classes is disclosed in 0 277,004 A1 of EP 0 277,003 A1 and EP, packet Include anion binding complex compound, the anion binding complex compound include multiple lipophilic groups covalently coordinating to and shielding center Electrically charged metal or metalloid core；With the anion comprising multiple boron atoms, such as carborane, metallocarborane and borine.

In an embodiment according to the present invention, the activator of stoichiometry includes cationic and the anionic component, And it can be indicated by following formula (1): (Z)_d ⁺(A^d-)(1)

Wherein Z is (L-H) or reducible lewis acid, and L is neutral Lewis base；H is hydrogen；(L-H)⁺For cloth Lanace platform Moral acid；A^d-For the non-coordinating anion with charge d-；The integer for being 1-3 with d.

When Z is (L-H) so that cationic components are (L-H)_d ⁺When, the cationic components may include Bronsted Acid, such as a part can be made, such as the protonated Lewis base of the protonation of the alkyl or aryl from catalyst precarsor, from And cationic transition metal species are generated, or the cation (L-H) of activation_d ⁺For Bronsted acid, it can give proton With catalyst precarsor, so that transition-metal cation is generated, including ammonium ion, Yang , Phosphonium, silicon and their mixing Object or methylamine, aniline, dimethyl amine, diethylamide, methylphenylamine, diphenylamine, Trimethylamine, triethylamine, N, N- bis- Methylaniline, methyldiphenyl base amine, pyridine, to bromine n,N-Dimethylaniline, to nitro-n,N-Dimethylaniline ammonium, three second Base phosphine, triphenylphosphine and diphenylphosphine Phosphonium, from ether (such as dimethyl ether Anaesthetie Ether), tetrahydrofuran and dioxanes Oxygen comes from the sulfonium and their mixture of thioether (such as diethyl thioether) and thiophane.

It, can be by formula: (Ar when Z is reducible lewis acid₃C⁺) indicate, wherein Ar is that aryl or hetero atom replace Aryl or C₁-C₄₀Alkyl, reducible lewis acid can be by formula: (Ph₃C⁺) indicate, wherein Ph is phenyl or hetero atom Substituted phenyl and/or C₁-C₄₀Alkyl.In an embodiment according to the present invention, reducible lewis acid is triphen Base carbon.

The anionic component A^d-Embodiment include have formula [M^k+Q_n]^d-Those of, wherein k is 1,2 or 3；N is 1,2, 3,4,5 or 6 or 3,4,5 or 6；N-k=d；Element and Q of the M in the 13rd race of the periodic table of elements or boron or aluminium independently are The dialkyl amide base of negative hydrogen ion, bridging or non-bridging, halogen ion, trialkylphosphine oxide, aromatic oxide, alkyl, the Q tool There are at most 20 carbon atoms, condition is that Q can form ring structure at a not more than appearance for halogen ion and two Q groups.Often One Q can for 1-20 carbon atom fluorination alkyl or every Q is fluoro aryl or every Q is five fluorine-based aryl.It closes Suitable A^d-The example of component further includes two boron compounds as disclosed in U.S. Patent number 5,447,895, by reference to full text It is incorporated herein.

In an embodiment according to the present invention, the present invention relates to the methods of olefin polymerization comprising by alkene (example Such as, ethylene and/or propylene) it is indicated with thio-salalen catalyst compounds, optional chain-transferring agent (CTA) and by formula (1) Boracic NCA activator contact, in which: Z be (L-H) or reducible lewis acid；L is neutral Lewis base (as more than It further describes)；H is hydrogen；It (L-H) is Bronsted acid (as further described above)；A^d-For with charge d^-'s Boracic non-coordinating anion (as further described above)；D is 1,2 or 3.

In an embodiment according to the present invention, in the NCA arbitrarily indicated by above-described formula 1, yin from Subgroup divides A^d-By formula [M*^k*+Q*_n*]^d*-It indicates, wherein k* is 1,2 or 3；N* is 1,2,3,4,5 or 6 (or 1,2,3 or 4)； N*-k*=d*；M* is boron；With Q* independently selected from negative hydrogen ion, the dialkyl amide base of bridging or non-bridging, halogen, alcoxyl Compound, fragrant oxide, alkyl, the Q* have at most 20 carbon atoms, and condition is that Q* is halogen at not more than 1 appearance.

The invention further relates to the methods of olefin polymerization comprising by alkene (such as ethylene and/or propylene) and as described above Thio-salalen catalyst compounds, optionally with CTA and by formula (2) indicate NCA activator contact: R_nM** (ArNHal)_4-n(2)

Wherein R is single anion ligand；M** is the 13rd race's metal or metalloid；ArNHal is halogenated, nitrogenous aromatic series Ring, Ppolynuclear aromatic ring or aromatic ring set, two of them or more ring (or fused ring system) is directly each other or together Connection；It is 0,1,2 or 3 with n.Typically, the NCA of the anion comprising formula 2 also includes not interfere by transition substantially suitably The cation for the ionic catalyst complex compound that metallic compound is formed, or cation are Z as described above_d ⁺。

It is anion-containing in the arbitrarily packet indicated by above-described formula 2 in an embodiment according to the present invention In NCA, R is selected from C₁-C₃₀Alkyl.In an embodiment according to the present invention, C₁-C₃₀Alkyl can be one or more C₁-C₂₀Alkyl, halogen ion, the organic quasi-metal that alkyl replaces, dialkyl amide base, alkoxy, aryloxy group, alkyl sulphur bridge (alkysulfido), aryl sulphur bridge (arylsulfido), alkyl phosphorus bridge (alkylphosphido), aryl phosphonium ion (arylphosphide) or other anion substituents；Fluorine ion；Huge alkoxide, wherein huge refer to C₄-C₂₀Hydrocarbon Base；--SR^a, -- NR^a ₂, and -- PR^a ₂Replace, wherein every R^aIt independently is C defined above₄-C₂₀Alkyl or C₄-C₂₀Alkyl takes The organic quasi-metal in generation.

It is anion-containing in the arbitrarily packet indicated by above-described formula 2 in an embodiment according to the present invention In NCA, NCA also includes cation, and the cation is comprising by formula: (Ar₃C⁺) reducible lewis acid for indicating, wherein Ar The aryl and/or C replaced for aryl or hetero atom₁-C₄₀Alkyl or reducible lewis acid are by formula: (Ph₃C⁺) indicate, Middle Ph is phenyl or the phenyl and/or C that are replaced by one or more hetero atoms₁-C₄₀Alkyl.

It is anion-containing in the arbitrarily packet indicated by above-described formula 2 in an embodiment according to the present invention In NCA, NCA also may include by formula (L-H)_d ⁺The cation of expression, wherein L is neutral Lewis base；H is hydrogen；It (L-H) is Blang Si Taide acid；It is 1,2 or 3 with d, or (L-H)_d ⁺For Bronsted acid, selected from ammonium, Yang, Phosphonium, silicon and theirs is mixed Close object.

The further example of available activator includes being disclosed in U.S. Patent number 7,297,653 and 7,799,879 Those, introduce herein by reference in by its full text.

In an embodiment according to the present invention, available activator includes the cation indicated by formula (3) herein The salt of type oxidant and noncoordinating, compatible anion:

(OX^e+)_d(A^d-)_e (3)

Wherein OX^e+For the cationic oxidant with charge e+；E is 1,2 or 3；D is 1,2 or 3；And A^d-For with The non-coordinating anion (as further described above) of charge d-.The example of cationic oxidant includes: ferrocene salt, hydrocarbon The substituted ferrocene salt of base-, Ag⁺Or Pb⁺²。A^d-Suitable embodiment include four (pentafluorophenyl group) borates.

In an embodiment according to the present invention, thio-salalen catalyst compounds described herein, optionally CTA's and/or NCA can be used together with huge activator." huge activator " used herein refers to by following formula table The anionic activator shown:

Wherein:

Every R₁It independently is halogen radical or fluorine-based；

Every R₂It independently is halogen, C₆-C₂₀Substituted aromatic hydrocarbyl or formula-O-Si-R_aSiloxy, wherein R_aFor C₁-C₂₀Alkyl or hy drocarbylsilyl (or R₂For fluorine-based or perfluorinated phenyl group)；

Every R₃For halogen, C₆-C₂₀Substituted aromatic hydrocarbyl or formula-O-Si-R_aSiloxy, wherein R_aFor C₁-C₂₀Hydrocarbon Base or hy drocarbylsilyl (or R₃For fluorine-based or C₆Perfluorinated aromatic alkyl)；Wherein R₂And R₃It can be formed one or more full And/or unsaturated, substituted or unsubstituted ring (or R₂And R₃Form perfluorinated phenyl group ring)；

L is neutral Lewis base；(L-H)⁺For Bronsted acid；D is 1,2 or 3；

Wherein anion has the molecular weight greater than 1020g/mol；With

Three substituent groups wherein at least on B atom respectively have greater than 250 cubic angstroms, or are greater than 300 cubic angstroms, or Greater than the molecular volume of 500 cubic angstroms.

As described above, " molecular volume " used herein as activator molecule in the solution space multistory size it is close Seemingly.The bulky substituent enumerated and their own conversion volume of suitable activator herein are shown in the following table and are divided Sub-volume.The expression of dotted line chemistry key is bonded on boron, as in formula above.

The huge activator enumerated that can be used for this paper catalyst system includes: trimethyl ammonium four (perfluoronapthyl) boric acid Salt, triethyl ammonium four (perfluoronapthyl) borate, tripropyl ammonium four (perfluoronapthyl) borate, three (normal-butyl) ammoniums, four (perfluor Naphthalene) borate, three (tert-butyl) ammonium four (perfluoronapthyl) borates, Ν, Ν-dimethylaniline four (perfluoronapthyl) boric acid Salt, Ν, Ν-diethylaniline four (perfluoronapthyl) borate, N, N- dimethyl-(2,4,6- trimethylaniline) four are (complete Fluoronaphthalene base) borate, tall and erect (tropillium) four (perfluoronapthyl) borate, triphenylcarbenium four (perfluoronapthyl) boric acid Salt, triphenyl phosphonium four (perfluoronapthyl) borate, triethyl-silicane four (perfluoronapthyl) borate, benzene (diazonium) four (perfluoronapthyl) borate, trimethyl ammonium four (perfluorinated biphenyl) borate, triethyl ammonium four (perfluorinated biphenyl) borate, three Propyl ammonium four (perfluorinated biphenyl) borate, three (normal-butyl) ammonium four (perfluorinated biphenyl) borates, three (tert-butyl) ammoniums four are (complete Fluorine xenyl) borate, Ν, Ν-dimethylaniline four (perfluorinated biphenyl) borate, Ν, Ν-diethylaniline four (perfluorinated biphenyl) borate, N, four (perfluorinated biphenyl) borate of N- dimethyl-(2,4,6- trimethylaniline), Zhuo Si (perfluorinated biphenyl) borate, triphenylcarbenium four (perfluorinated biphenyl) borate, triphenyl phosphonium four (perfluorinated biphenyl) boric acid Salt, triethyl-silicane four (perfluorinated biphenyl) borate, benzene (diazonium) four (perfluorinated biphenyl) borate, [the tertiary fourth of 4- Base-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the type disclosed in United States Patent (USP) No.7,297,653, it is logical herein It crosses and is introduced with reference to full text.

The schematic of the boron compound of activator, but non-limiting example can be used as in the method for the disclosure of invention It include: trimethyl ammonium tetraphenyl borate salts, triethyl ammonium tetraphenyl borate salts, tripropyl ammonium tetraphenyl borate salts, three (positive fourths Base) ammonium tetraphenyl borate salts, three (tert-butyl) ammonium tetraphenyl borate salts, Ν, Ν-dimethylaniline tetraphenyl borate salts, Ν, Ν-diethylaniline tetraphenyl borate salts, N, N- dimethyl-(2,4,6- trimethylaniline) tetraphenyl borate salts are tall and erect Tetraphenyl borate salts, triphenylcarbenium tetraphenyl borate salts, triphenyl phosphonium tetraphenyl borate salts, triethyl-silicane tetraphenyl Borate, benzene (diazonium) tetraphenyl borate salts, trimethyl ammonium four (pentafluorophenyl group) borate, triethyl ammonium four (pentafluorophenyl group) Borate, tripropyl ammonium four (pentafluorophenyl group) borate, three (normal-butyl) ammonium four (pentafluorophenyl group) borates, three (sec-butyl) ammoniums Four (pentafluorophenyl group) borates, Ν, Ν-dimethylaniline four (pentafluorophenyl group) borate, Ν, Ν-diethylaniline four (pentafluorophenyl group) borate, N, four (pentafluorophenyl group) borate of N- dimethyl-(2,4,6- trimethylaniline), Zhuo Si (five Fluorophenyl) borate, triphenylcarbenium four (pentafluorophenyl group) borate, triphenyl phosphonium four (pentafluorophenyl group) borate, triethyl group Monosilane four (pentafluorophenyl group) borate, benzene (diazonium) four (pentafluorophenyl group) borate, trimethyl ammonium four-(2,3,4,6- Tetrafluoro phenyl) borate, triethyl ammonium four-(2,3,4,6- tetrafluoro phenyl) borate, tripropyl ammonium four-(2,3,4,6- tetrafluoros Phenyl) borate, three (normal-butyl) ammoniums, four-(2,3,4,6- tetrafluoro phenyl) borate, dimethyl (tert-butyl) ammonium four-(2,3, 4,6- tetrafluoro phenyl) borate, Ν, Ν-dimethylaniline four-(2,3,4,6- tetrafluoro phenyl) borate, Ν, Ν-diethyl Base aniline four-(2,3,4,6- tetrafluoro phenyl) borate, N, N- dimethyl-(2,4,6- trimethylaniline) four-(2,3,4, 6- tetrafluoro phenyl) borate, Zhuo Si-(2,3,4,6- tetrafluoro phenyl) borate, triphenylcarbenium four-(2,3,4,6- tetrafluoros Phenyl) borate, triphenyl phosphonium four-(2,3,4,6- tetrafluoro phenyl) borate, triethyl-silicane four-(2,3,4,6- tetra- Fluorophenyl) borate, benzene (diazonium) four-(2,3,4,6- tetrafluoro phenyl) borate, trimethyl ammonium four (perfluoronapthyl) boric acid Salt, triethyl ammonium four (perfluoronapthyl) borate, tripropyl ammonium four (perfluoronapthyl) borate, three (normal-butyl) ammoniums, four (perfluor Naphthalene) borate, three (tert-butyl) ammonium four (perfluoronapthyl) borates, Ν, Ν-dimethylaniline four (perfluoronapthyl) boric acid Salt, Ν, Ν-diethylaniline four (perfluoronapthyl) borate, N, N- dimethyl-(2,4,6- trimethylaniline) four are (complete Fluoronaphthalene base) borate, Zhuo Si (perfluoronapthyl) borate, triphenylcarbenium four (perfluoronapthyl) borate, triphenyl phosphonium four (perfluoronapthyl) borate, triethyl-silicane four (perfluoronapthyl) borate, benzene (diazonium) four (perfluoronapthyl) boric acid Salt, trimethyl ammonium four (perfluorinated biphenyl) borate, triethyl ammonium four (perfluorinated biphenyl) borate, four (perfluor of tripropyl ammonium Xenyl) borate, three (normal-butyl) ammonium four (perfluorinated biphenyl) borates, three (tert-butyl) ammonium four (perfluorinated biphenyl) boric acid Salt, Ν, Ν-dimethylaniline four (perfluorinated biphenyl) borate, Ν, Ν-diethylaniline four (perfluorinated biphenyl) boron Hydrochlorate, N, four (perfluorinated biphenyl) borate of N- dimethyl-(2,4,6- trimethylaniline), Zhuo Si (perfluorinated biphenyl) boron Hydrochlorate, triphenylcarbenium four (perfluorinated biphenyl) borate, triphenyl phosphonium four (perfluorinated biphenyl) borate, triethyl-silicane Four (perfluorinated biphenyl) borates, benzene (diazonium) four (perfluorinated biphenyl) borate, (3, the 5- bis- (trifluoros of trimethyl ammonium four Methyl) phenyl) borate, triethyl ammonium four (3,5- bis- (trifluoromethyl) phenyl) borate, tripropyl ammonium four (3,5- bis- (three Methyl fluoride) phenyl) borate, three (normal-butyl) ammonium four (3,5- bis- (trifluoromethyl) phenyl) borates, three (tert-butyl) ammoniums four (3,5- bis- (trifluoromethyl) phenyl) borate, Ν, Ν-dimethylaniline four (3,5- bis- (trifluoromethyl) phenyl) boric acid Salt, Ν, Ν-diethylaniline four (3,5- bis- (trifluoromethyl) phenyl) borate, N, N- dimethyl-(2,4,6- trimethyls Aniline) four (3,5- bis- (trifluoromethyl) phenyl) borates, Zhuo Si (3,5- bis- (trifluoromethyl) phenyl) borate, triphen Base carbon four (3,5- bis- (trifluoromethyl) phenyl) borate, triphenyl phosphonium four (3,5- bis- (trifluoromethyl) phenyl) borate, Triethyl-silicane four (3,5- bis- (trifluoromethyl) phenyl) borate, (3,5- bis- (trifluoromethyl) benzene of benzene (diazonium) four Base) borate and dialkyl ammonium, such as: two-(isopropyl) ammoniums, four (pentafluorophenyl group) borate and (five fluorine of dicyclohexyl ammonium four Phenyl) borate；Replace phosphonium salt, such as three (four (pentafluorophenyl group) borate of o- tolyl) Phosphonium and three with additional three- (four (pentafluorophenyl group) borate of 2,6- 3,5-dimethylphenyl) Phosphonium.

Suitable activator includes: Ν, Ν-dimethylaniline four (perfluoronapthyl) borate, Ν, Ν-dimethyl benzene Amine four (perfluorinated biphenyl) borate, Ν, Ν-dimethylaniline four (3,5- bis- (trifluoromethyl) phenyl) borate, three Phenyl carbons four (perfluoronapthyl) borate, triphenylcarbenium four (perfluorinated biphenyl) borate, (3,5- is bis- for triphenylcarbenium four (trifluoromethyl) phenyl) borate, triphenylcarbenium four (perfluorophenyl) borate, [Ph₃C⁺][B(C₆F₅)₄ ^-], [Me₃NH⁺][B (C₆F₅)₄ ^-]；1- (4- (three (pentafluorophenyl group) borates) -2,3,5,6- tetrafluoro phenyl) pyrrolidines；Four (pentafluorophenyl group) boric acid Salt and 4- (three (pentafluorophenyl group) borates) -2,3,5,6- ptfe pyridines.

In an embodiment according to the present invention, activator includes triaryl carbon (such as four benzene of triphenylcarbenium Ylboronic acid salt, triphenylcarbenium four (pentafluorophenyl group) borate, triphenylcarbenium four-(2,3,4,6- tetrafluoro phenyl) borate, Triphenylcarbenium four (perfluoronapthyl) borate, triphenylcarbenium four (perfluorinated biphenyl) borate, triphenylcarbenium four (3,5- Bis- (trifluoromethyl) phenyl) borate).

In an embodiment according to the present invention, activator includes one or more of (five fluorine of trialkyl ammonium four Phenyl) borate, Ν, Ν-dialkyl aniline four (pentafluorophenyl group) borate, N, N- dimethyl-(2,4,6- trimethylanilines ) four (pentafluorophenyl group) borates, trialkyl ammonium four-(2,3,4,6- tetrafluoro phenyl) borate, Ν, Ν-dialkyl aniline Four-(2,3,4,6- tetrafluoro phenyl) borates, trialkyl ammonium four (perfluoronapthyl) borate, Ν, Ν-dialkyl aniline four (perfluoronapthyl) borate, trialkyl ammonium four (perfluorinated biphenyl) borate, Ν, four (perfluorinated biphenyl of Ν-dialkyl aniline Base) borate, trialkyl ammonium four (3,5- bis- (trifluoromethyl) phenyl) borate, Ν, (3,5- is bis- for Ν-dialkyl aniline four (trifluoromethyl) phenyl) borate, N, N- dialkyl group-(2,4,6- trimethylaniline) four (3,5- bis- (trifluoromethyl) phenyl) Borate, two-(isopropyl) ammonium four (pentafluorophenyl group) borates, wherein alkyl is methyl, ethyl, propyl, normal-butyl, sec-butyl Or tert-butyl.

In an embodiment according to the present invention, tied with catalyst compounds and/or optional CTA and/or NCA Before or after conjunction, or before mixing with catalyst compounds and/or optional CTA and/or NCA, this can be mixed together Any activator of text description.

It, can be living using two kinds of NCA activators and the first NCA in polymerization in an embodiment according to the present invention Agent and the molar ratio of the 2nd NCA activator can be any ratio.In an embodiment according to the present invention, first The molar ratio of NCA activator and the 2nd NCA activator is 0.01:1 to 10, and 000:1 or 0.1:1 to 1000:1 or 1:1 are arrived 100:1。

In an embodiment according to the present invention, NCA activator is molar ratio 1:1 or 0.1:1 to the ratio between catalyst To 100:1 or 0.5:1 to 200:1 or 1:1 to 500:1 or 1:1 to 1000:1.In an embodiment according to the present invention In, NCA activator is 0.5:1 to 10:1 or 1:1 to 5:1 to the ratio between catalyst.

In an embodiment according to the present invention, in combination with the combination of the catalyst compounds and aikyiaiurnirsoxan beta and NCA Object (see, e.g. US 5,153,157, US 5,453,410, EP0 573120 Bl, WO 94/07928 and WO 95/ 14044, they discuss and aikyiaiurnirsoxan beta are used in combination with ionization activator, all these herein by reference in introducing).

Useful chain-transferring agent is typically alkylaluminoxane, with formula AlR₃, ZnR₂(wherein every R is only for the compound of expression It is on the spot C₁-C₈Aliphatic group, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, octyl or its isomers) or combinations thereof, Such as diethyl zinc, methylaluminoxane, trimethyl aluminium, triisobutyl aluminium, trioctylaluminum, or combinations thereof.

Scavenger or activator promotor

In an embodiment according to the present invention, catalyst system can further comprise scavenger and/or help activation Agent.The suitable alkyl aluminum or organic group aluminium compound that can be used as scavenger or activator promotor include such as trimethyl aluminium, three second Base aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium and analog.Other oxyphie (oxophilic) species can be used, Such as diethyl zinc.

Catalyst carrier

In an embodiment according to the present invention, catalyst system may include inert support material.According to this hair In a bright embodiment, carrier material includes porous carrier materials, such as talcum and/or inorganic oxide.Other are suitable Carrier material include zeolite, clay, organic clay or any other organic or inorganic carrier material and analog or it is mixed Close object.

In an embodiment according to the present invention, carrier material is the inorganic oxide of fine form.This paper's Suitable inorganic oxide material used in catalyst system includes the 2nd, 4,13 and 14 family metal oxide, such as is aoxidized Silicon, aluminium oxide and its mixture.Can or individually or other inorganic oxides for being used in combination with silica and/or aluminium oxide Object includes magnesia, titanium oxide, zirconium oxide, montmorillonite, phyllosilicate and/or analog.Other suitable carrier materials include Fine functionalised polyolefin, such as fine polyethylene.

In an embodiment according to the present invention, the surface area of carrier material can be about 10- about 700m²/ G, range of hole volume is about 0.1- about 4.0cc/g and mean particle size range is the surface area of about 500 μm of about 5- or carrier material Range is about 50- about 500m²/ g, pore volume is about 0.5- about 3.5cc/g and average particle size is about 200 μm of about 10-.According to this In one embodiment of invention, most of range of the surface area of carrier material is about 100- about 400m²/ g, pore volume are about 0.8- about 3.0cc/g and average particle size are about 100 μm of about 5-.In an embodiment according to the present invention, carrier material Average cell size range is 10-1000 angstroms or 50- about 500 angstroms or about 350 angstroms of 75-.In an embodiment according to the present invention In, carrier material is surface area greater than or equal to about 300m²/ g and/or pore volume are 1.65cm³The high surface area of/g it is amorphous Silica.Suitable silica is with trade name Davison 952 or Davison 955 by Davison Chemical Division of W.R.Grace and Company is commercially available.In an embodiment according to the present invention, carrier material can Including Davison 948.

In an embodiment according to the present invention, carrier material should be essentially dry, that is to say, that does not have substantially There is the water of absorption.It can be by about 100 DEG C-about 1000 DEG C, or at least about 400 DEG C or 500 DEG C or 600 DEG C of temperature Lower heating or calcining, carry out the drying of carrier material.When carrier material is silica, through about 1 minute-about 100 hours, or about 12 hours-about 72 hours, or it is heated within about 24 hours-about 60 hours at least 200 DEG C, or about 200 DEG C-about 850 DEG C, or at least 600℃.In an embodiment according to the present invention, burnt carrier material must have at least some reactive hydroxyls (OH), to produce the catalyst system of the carrying of disclosure according to the present invention.

In an embodiment according to the present invention, burnt carrier material and the catalyst containing at least one are contacted Close at least one polymerization catalyst of object and activator.In an embodiment according to the present invention, in nonpolar solvent It is slurried that there is reactive surfaces group, the typically carrier material of hydroxyl, and contact gained slurries and catalyst compounds and The solution of activator.In an embodiment according to the present invention, slurries and activator of contact carrier material first, at that time Between segment limit be about 0.5 hour-about 24 hours, or about 2 hours-about 16 hours, or about 4 hours-about 8 hours.Then contact should The solution of catalyst compounds and isolated carrier/activator.In an embodiment according to the present invention, in-situ generation is held The catalyst system of load.In alternate embodiment, the slurries of carrier material are contacted with catalyst compounds first, the time Segment limit is about 0.5 hour-about 24 hours, or about 2 hours-about 16 hours, or about 4 hours-about 8 hours.Then what is carried urges The slurries of agent compound are contacted with activator solution.

In an embodiment according to the present invention, heatable catalyst, the mixture of activator and carrier to about 0 DEG C- About 70 DEG C, perhaps to about 23 DEG C-about 60 DEG C or to 25 DEG C (room temperature).Contact time range be typically about 0.5 hour-about 24 hours, or about 2 hours-about 16 hours, or about 4 hours-about 8 hours.

Suitable nonpolar solvent is that wherein all reactants used herein, i.e. activator and catalyst compounds be extremely Small part is solvable and is at the reaction temperatures the material of liquid.Suitable nonpolar solvent includes alkane, such as isopentane, oneself Alkane, normal heptane, octane, nonane and decane, although various other materials can also be used, including cycloalkane, such as hexamethylene, Aromatic hydrocarbons, such as benzene, toluene and ethylbenzene.

Polymerization

In an embodiment according to the present invention, polymerization includes contact monomer (such as ethylene and propylene), and Optionally comonomer and the above-described catalyst system containing activator and at least one catalyst compounds.According to this In one embodiment of invention, can combined catalyst compound and activator in any sequence, and can be contacted with monomer It combines before.In an embodiment according to the present invention, after being contacted with monomer, combined catalyst compound and/or Activator.

In an embodiment according to the present invention, the method for olefin polymerization includes under polymerization conditions, contacting one kind Or a variety of alkene and catalyst system, polyolefin is produced, wherein the catalyst system includes activator and urged with what following formula indicated Agent compound:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

In an embodiment according to the present invention, catalyst includes the [O of fac-mer arrangement¹,N,S]-[N,S,O²]； Or in which the activation of catalyst compounds makes [O¹,N,S]-[N,S,O²] it is rearranged to fac-mer arrangement.In another embodiment, Catalyst includes the [O of mer-fac arrangement¹,N,S]-[N,S,O²]；Or in which the activation of catalyst compounds makes [O¹,N,S]- [N,S,O²] it is rearranged to mer-fac arrangement.In another embodiment, catalyst includes the [O of fac-fac arrangement¹,N,S]-[N, S,O²]；Or in which the activation of catalyst compounds makes [O¹,N,S]-[N,S,O²] it is rearranged to fac-fac arrangement.

It, can be before activation of catalyst, before with or without separating catalyst in an embodiment according to the present invention It is raw in conjunction with thio-salalen ligand and metalating agent in the case where body, or with activation simultaneously and/or in the presence of monomer The catalyst precarsor of pan category di-substituted, so that catalyst is formed in situ during polymerization technique.At one according to the present invention In embodiment, the method for olefin polymerization can include:

Thio-salalen ligand and metalating agent are contacted, catalyst precarsor is produced；With

Under polymerization conditions, the catalyst precarsor and activator and one or more alkene are contacted, polyolefin is produced；

Wherein thio-salalen ligand is indicated with following formula:

Wherein metalating agent is indicated with following formula: MX¹X²X³X⁴

Wherein catalyst precarsor is indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race, however, condition is the then X in the case where M is trivalent²It does not deposit ?；

Wherein every X¹And X²It independently is monovalent C₁-C₂₀Alkyl, the official containing the element of 13-17 race in the periodic table of elements It can group or X¹And X²(if present) it connects together, forms C₄-C₆₂Cyclic annular or polycyclic ring structure；

In an embodiment according to the present invention, it can contact thio-salalen before in conjunction with activator and match Body and metalating agent, and then in the case where no separating catalyst precursor, or with activation simultaneously and/or in monomer presence Under, it is contacted with activator, so that catalyst is formed in situ during polymerization technique.In an embodiment according to the present invention In, can in the presence of an activator, in the presence of one or more alkene, or a combination thereof under, for example, polymerization technique in situ In, contact thio-salalen ligand and metalating agent.

Monomer useful herein includes substituted or unsubstituted C₂-C₄₀Alhpa olefin or C₂-C₂₀Alhpa olefin or C₂-C₁₂Alhpa olefin, Or ethylene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, endecatylene, dodecylene and its isomers.? In an embodiment according to the present invention, monomer includes propylene and optional comonomer, and the comonomer includes one Kind or more ethylene or C₄-C₄₀Alkene or C₄-C₂₀Alkene or C₆-C₁₂Alkene.C₄-C₄₀Olefinic monomer can be straight chain, branch Chain is cricoid.C₄-C₄₀Cyclic olefin can be tensioning (strained) or untensioned, monocycle or polycyclic, and optionally Including hetero atom and/or one or more functional groups.According to an embodiment of the invention, monomer includes ethylene or second Alkene and comonomer, the comonomer include one or more C₃-C₄₀Alkene or C₄-C₂₀Alkene or C₆-C₁₂Alkene. C₃-C₄₀Olefinic monomer can be chain, branch or cricoid.C₃-C₄₀Cyclic olefin can be tensioning or it is untensioned, monocycle or It is polycyclic, and optionally include hetero atom and/or one or more functional groups.

The C enumerated₂-C₄₀Olefinic monomer and optional comonomer include ethylene, propylene, butylene, amylene, hexene, heptene, Octene, nonene, decene, endecatylene, dodecylene, norbornene, norbornadiene, bicyclopentadiene, cyclopentene, cycloheptyl Alkene, cyclo-octene, cyclo-octadiene, cyclodecene, 7- oxanorbornene, 7- oxanorbornadiene, substitutive derivative and they Isomers or hexene, heptene, octene, nonene, decene, dodecylene, cyclo-octene, 1,5- cyclo-octadiene, 1- hydroxyl -4- Cyclo-octene, 1- acetoxyl group -4- cyclo-octene, 5- methyl cyclopentene, cyclopentene, bicyclopentadiene, norbornene, norborneol two Alkene and their own analogs and derivatives or norbornene, norbornadiene and bicyclopentadiene.

In an embodiment according to the present invention, there are most 10wt% in the polymer that produces herein, or One or more of alkadienes of 0.00001-1.0wt% perhaps 0.002-0.5wt% or 0.003-0.2wt%, are based on The total weight of composition.In an embodiment according to the present invention, addition is less than or equal to 500ppm, or is less than or waits Alkadienes in 400ppm, or less than or equal to 300ppm is into polymerization.In an embodiment according to the present invention, add Few 50ppm is added to, 100ppm is perhaps greater than or equal to or is greater than or equal to 150ppm alkadienes into polymerization.

Diolefinic monomer for use in the present invention includes any hydrocarbon structure or C at least two unsaturated bonds₄-C₃₀, Wherein at least two unsaturated bond passes through or three-dimensional special or non-stereospecific catalyst, is easy to be incorporated into polymer It is interior.In an embodiment according to the present invention, diolefinic monomer can be selected from α, and ω-diolefinic monomer is (that is, two-vinyl Monomer).More diolefinic monomer is two-vinyl monomer of straight chain, and most most is containing those of 4-30 carbon atom.Alkadienes Example include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon Diene, oleatridecadiene, 14 carbon diene, pentadecane diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon Diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, two pentadecanes Diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, 1,6- heptan two Alkene, 1,7- octadiene, 1,8- nonadiene, 1,9- decadinene, 1,10- ten one carbon diene, 1,11- ten two carbon diene, 1,12- ten three Carbon diene, 1,13- ten four carbon diene and low molecular weight polybutadiene (Mw is less than 1000g/mol).Cyclic diene includes ring penta 2 Alkene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinylbenzene, bicyclopentadiene or in each ring position The more advanced ring containing alkadienes with or without substituent group.

In an embodiment according to the present invention, in the case where butylene is comonomer, butylene source, which can be, to be contained The mixed butene logistics of various butylene isomers.It is expected that 1- butene monomers are preferably consumed by polymerization technique.Use this mixing fourth Alkene logistics will provide economic advantages, because these mixture flows are often the waste stream from refinery practice, such as C₄Raffinate Logistics, and therefore can be significantly so expensive not as good as pure 1- butylene.

In an embodiment according to the present invention, one or more alkene include propylene.

The polymerization of disclosure according to the present invention can be carried out according to any mode known in the art.This can be used Any suspension known to field, homogeneously, ontology, solution, slurry or gaseous polymerization.These methods can interval, semi-batch or It is carried out under continuous mode.Homogeneous polymerization process and slurry process are suitable for used herein, and wherein homogeneous polymerization process is defined as it In at least product of 90wt% soluble technique in reaction medium.Ontology homogeneous method be suitable for it is used herein, wherein this Body method is defined as the technique that wherein monomer concentration is greater than or equal to 70 volume % in reaching all raw materials in reactor.? In an embodiment according to the present invention, be not present solvent or diluent, or in reaction medium without addition solvent or Diluent (except that the catalyst system used in a small amount or other additive carriers, or typically with one starting of monomer Existing dosage, such as the propane in propylene).In an embodiment according to the present invention, this method is slurry process.Herein Used term " slurry polymerization process " refers to wherein polymerize list using the catalyst of carrying and on the catalyst granules of carrying The polymerization of body.At least 95wt% polymer product as derived from the catalyst carried is the granular form as solid particle (not being dissolved in diluent).

Suitable diluent/solvent for polymerization includes the inert fluid of non-coordination.Example includes straight chain and branch Hydrocarbon, such as iso-butane, butane, pentane, isopentane, hexane class, isohexane, heptane, octane, dodecane and its mixture；It is cyclic annular And clicyclic hydrocarbon, for example, hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane and its mixture, such as can be commercially It was found that those of (Isopar^TM)；Perhalogenation hydrocarbon, such as perfluorinated C_4-10Alkane, chlorobenzene and aromatic hydrocarbons and alkyl-substituted aromatics Compound, such as benzene, toluene, 1,3,5- trimethylbenzene and dimethylbenzene.Suitable solvent further includes liquid olefin, they can be filled When monomer or comonomer, including ethylene, propylene, 1- butylene, 1- hexene, 1- amylene, 3- Methyl-1-pentene, 4- methyl- 1- amylene, 1- octene, 1- decene and its mixture.In an embodiment according to the present invention, aliphatic hydrocarbon solvent is used as molten Agent, such as iso-butane, butane, pentane, isopentane, hexane class, isohexane, heptane, octane, dodecane and its mixture；It is cyclic annular And clicyclic hydrocarbon, such as hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane and its mixture.According to the present invention In one embodiment, solvent is not aromatic hydrocarbons or aromatic hydrocarbons to be less than 1wt%, or is less than 0.5wt%, or less than 0.0wt%'s Dosage is present in solvent, solvent-based weight.

In an embodiment according to the present invention, it is less than for the monomer of polymerization and the material concentration of comonomer Or it is equal to 60vol% solvent, or be less than or equal to 40vol%, or be less than or equal to 20vol%, the totality based on feed stream Product.Or it is polymerize in substance law.

It can be polymerize in the case where being suitable for obtaining required polyvinyl any temperature and/or pressure.Suitable temperature And/or it is about 0 DEG C-about 300 DEG C that pressure, which includes range, or about 20 DEG C-about 200 DEG C, or about 35 DEG C-about 150 DEG C, or about 40 DEG C- About 120 DEG C, or about 45 DEG C-about 80 DEG C of temperature and range is about 0.35MPa- about 10MPa, or about 0.45MPa- about 6MPa, or The pressure of about 0.5MPa- about 4MPa.

In an embodiment according to the present invention, the progress time of reaction is about 0.1 minute-about 24 hours, or most More 16 hours or range are about 5-250 minutes, or about 10-120 minutes.

In an embodiment according to the present invention, hydrogen is with 0.001-50psig (0.007-345kPa) or 0.01- The partial pressure of 25psig (0.07-172kPa) or 0.1-10psig (0.7-70kPa) are present in polymer reactor.

In an embodiment according to the present invention, polymerizing condition includes about 0 DEG C-about 300 DEG C of temperature, about The pressure of 0.35MPa- about 10MPa, and about 0.1 minute-about 24 hours time.

In an embodiment according to the present invention, the activity of catalyst is at least 50g/mmol/hr, or is greater than or waits In 500g/mmol/hr, or it is greater than or equal to 5000g/mmol/hr, or is greater than or equal to 50,000g/mmol/hr.Alternative In embodiment, the conversion ratio of olefinic monomer is at least 10%, based on polymer yield and enters the monomer weight in reaction zone Amount, or it is greater than or equal to 20%, or be greater than or equal to 30%, or be greater than or equal to 50%, or be greater than or equal to 80%.

In an embodiment according to the present invention, polymerizing condition includes one or more in following: 1) temperature 0-300 DEG C (or 25-150 DEG C or 40-120 DEG C or 45-80 DEG C)；2) pressure be atmosphere be pressed onto 10MPa (or 0.35-10MPa, Or 0.45-6MPa or 0.5-4MPa)；3) there are aliphatic hydrocarbon solvent (for example, iso-butane, butane, pentane, isopentane, hexane class, Isohexane, heptane, octane, dodecane and its mixture；Cyclic annular and clicyclic hydrocarbon, such as hexamethylene, cycloheptane, methyl cyclohexane Alkane, methylcycloheptane and its mixture；Or in the case where aromatic hydrocarbons, to be less than 1wt%, or it is less than 0.5wt%, or in 0wt% Under be present in solvent, solvent-based weight)；4) wherein the catalyst system used in polymerization includes being less than 0.5mol% or 0mol% aikyiaiurnirsoxan beta or aikyiaiurnirsoxan beta are less than 500:1 with molar ratio of the aluminium to transition metal, or are less than 300:1, Or it is less than 100:1, or be less than 1:1 and exist；5) it polymerize in a reaction zone；6) productivity of catalyst compounds is extremely Few 80,000g/mmol/hr (or at least 150,000g/mmol/hr, or at least 200,000g/mmol/hr, or at least 250, 000g/mmol/hr, or at least 300,000g/mmol/hr)；7) there is no scavenger (for example, trialkyl aluminium compound) (such as With 0mol% presence) or with scavenger than transition metal molar ratio be less than 100:1, or be less than 50:1, or be less than 15:1, or Less than 10:1, there are scavengers；And/or 8) in polymer reactor with 0.007-345kPa (0.001-50psig) (or 0.07- 172kPa (0.01-25psig) or 0.7-70kPa (0.1-10psig)) partial pressure be optionally present hydrogen.

In an embodiment according to the present invention, the catalyst system used in polymerization includes no more than one kind Catalyst compounds." reaction zone " is also referred to as " polymeric area ", is the container wherein polymerizeing, such as batch reactor.When making With or series connection or plan-parallel structure multiple reactors when, each reactor is considered as independent polymeric area.For in interval For multi-stage polymeric in reactor and flow reactor the two, each polymeric segment is considered as independent polymeric area.According to this In one embodiment of invention, it polymerize in a reaction zone.

In an embodiment according to the present invention, the method for olefin polymerization includes under polymerization conditions, contacting one kind Or the catalyst system of any one of a variety of alkene and embodiment disclosed herein or combinations thereof, produce polyolefin.

In a special embodiment, polymerizing condition includes about 0 DEG C-about 300 DEG C of temperature, and about 0.35MPa- is about The pressure of 10MPa, and about 0.1 minute-about 24 hours time.It is a kind of or more in an embodiment according to the present invention Kind alkene includes propylene.In an embodiment according to the present invention, polypropylene includes at least 50mol% propylene.

Polyolefin product

The disclosure further relates to the composition of matter produced by method described herein.

In an embodiment according to the present invention, method described herein produce Mw/Mn be greater than 1 to 4 (or be greater than 1 To Noblen or propylene copolymer 3), such as propylene-ethylene and/or propylene-alpha-olefin (or C₃-C₂₀) copolymer (example Such as, butene-hexene copolymer or propylene-octene Copolymer).

Equally, method of the invention production olefin polymer or polyethylene and polypropylene homopolymer and copolymer.In basis In one embodiment of the invention, the polymer produced herein is the homopolymer of ethylene or propylene, be ethylene or have 0- One or more of C of 25mol% (or 0.5-20mol% or 1-15mol% or 3-10mol%)₃-C₂₀Olefin comonomer (or C₃-C₁₂Alpha-olefin or propylene, butylene, hexene, octene, decene, dodecylene or propylene, butylene, hexene, octene) be total to Polymers or propylene have 0-25mol% (or 0.5-20mol% or 1-15mol% or 3-10mol%) a kind of or more A variety of C₂Or C₄-C₂₀Olefin comonomer (or ethylene or C₄-C₁₂Alpha-olefin or ethylene, butylene, hexene, octene, decene, 12 Carbene or ethylene, butylene, hexene, octene) copolymer.

In an embodiment according to the present invention, the Mw of the polymer produced herein is 5,000-1,000,000g/ Mol (for example, 25,000-750,000g/mol or 50,000-500,000g/mol) and/or Mw/Mn be greater than 1 to 40, or 1.2-20 or 1.3-10 or 1.4-5 or 1.5-4 or 1.5-3.

In an embodiment according to the present invention, the polymer produced herein is with unimodal or multimodal molecular weight point Cloth, this is measured by gel permeation chromatography (GPC)." unimodal " refers to that GPC curve has a peak or inflection point." bimodal " is Refer to that GPC curve has at least two peaks or inflection point.Inflection point is the sign of the flection (derivative) of wherein curve (sign) point changed (for example, from negative to positive or on the contrary).

Unless otherwise indicated, by US 2006/0173123, the 24-25 pages, described in [0334]-[0341] section GPC measures Mw, Mn, MWD.

In an embodiment according to the present invention, one or more alkene include propylene.According to the present invention one In a embodiment, polyolefin includes including at least 50mol% propylene, preferably at least 75mol% propylene, preferably at least 85mol% propylene.In an embodiment according to the present invention, polyolefin has greater than or equal to about 50wt%, or 60wt% or 70wt% or 80wt% or 90wt%, or meso isotaxy Unit five greater than or equal to about 99wt% Group [mmmm] concentration, the total weight based on polymer.

In an embodiment according to the present invention, polyolefin has greater than or equal to about 50wt% or 60wt%, or 70wt% or 80wt% or 90wt%, or the five unit group [mmmm] of meso isotaxy greater than or equal to about 99wt% are dense Degree, the total weight based on polymer, this passes through¹³C NMR measurement.

Polyacrylic polymer preferably has a degree of isotacticity, and preferably isotactic polypropylene or Height isotactic polypropylene." isotaxy " used herein is defined as basis¹³The analysis of C NMR has at least 10% isotaxy, five unit group." height isotaxy " used herein is defined as basis¹³The analysis of C NMR, has Five unit group of at least 60% isotaxy.

Polyacrylic polymer can have more than or equal to 90%, be greater than or equal to 92%, be greater than or equal to 94%, be greater than or Equal to 95%, it is greater than or equal to 96%, is greater than or equal to 97%, or the two unit group of propylene meso more than or equal to 98% Content.The isotacticity of polyacrylic polymer can pass through¹³C NMR measurement.For example, measurement polyacrylic polymer is complete same The appropriate technology of steric regularity can be as discussed in United States Patent (USP) No.:4,950,720 and described in.In another way Expression, in certain embodiments, passes through¹³C NMR measurement and with five pentad contents express polyacrylic polymer it is complete together Steric regularity is greater than 93% or 95% or 97%.

Fusing heat (the H of the polymer produced herein_f, second of heating of DSC) and it may be greater than or be equal to 50J/g, Preferably greater than or equal to 60J/g, preferably greater than or equal to 70J/g, preferably greater than or equal to 80J/g, preferably greater than or equal to 90J/g, preferably greater than or equal to 95J/g, or preferably greater than or equal to about 100J/g.

In an embodiment according to the present invention, polyolefin includes at least 50mol% isotactic polypropylene, and makes The fusing point T measured with differential scanning calorimetry_MeltingGreater than about 145 DEG C, for example, about 145 DEG C-about 170 DEG C, or about 145 DEG C-about 165℃.In an embodiment according to the present invention, within the scope of this, the fusing point T of polyolefin_MeltingGreater than or equal to about 148 DEG C, perhaps greater than or equal to about 150 DEG C perhaps greater than or equal to about 152 DEG C or greater than or equal to about 154 DEG C, or it is big In or equal to about 155.5 DEG C.In some embodiments of the present invention, the fusing point T of polyolefin_MeltingLess than or equal to about 175 DEG C, Perhaps less than or equal to about 170 DEG C perhaps less than or equal to about 165 DEG C or less than or equal to about 160 DEG C, or it is less than or waits In about 157 DEG C, or less than or equal to about 156 DEG C.

In an embodiment according to the present invention, polyolefin includes at least 50mol% propylene.It is special real at one Apply in scheme, polyolefin include at least five unit group [mmmm] concentration of 50mol% meso isotaxy greater than or equal to about The propylene of 90wt%.In some embodiments, polyolefin includes being greater than 95wt% isotactic polypropylene, or be greater than 96wt% Isotactic polypropylene, or it is greater than 97wt% isotactic polypropylene, or be greater than 98wt% isotactic polypropylene, at most 99.9wt% isotactic polypropylene, the weight based on polyolefin.In special embodiment, polyolefin includes being greater than 95wt% isotactic polypropylene, and fusing point is greater than or equal to about 150 DEG C or in which polyolefin includes being greater than 98wt% entirely with vertical Structure polypropylene, and fusing point is greater than or equal to about 155 DEG C.

Blend

In an embodiment according to the present invention, in conjunction with the polymer (or polyethylene or polypropylene) that produces herein with One or more of additional polymer, are formed as film, molded parts or other products later.Other useful polymer packets Include polyethylene, isotactic polypropylene, height isotactic polypropylene, syndiotactic polypropylene, propylene and ethylene and/or fourth The random copolymer of alkene and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate Ester, ethylene methyl acrylate, the copolymer of acrylic acid, polymethyl methacrylate, or it is polymerizable by high-pressure free radical process Any other polymer, polyvinyl chloride, PB Polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), sulphur Change EPR, EPDM, block copolymer, styrene block copolymers, polyamide, polycarbonate, PET resin, crosslinked polyethylene, The copolymer of ethylene and vinyl alcohol (EVOH), the polymer of aromatic monomer, such as polystyrene, polyester, polyacetals, polyvinylidene fluoride Alkene, polyethylene glycol and/or polyisobutene.

In an embodiment according to the present invention, with 10-99wt% or 20-95wt% in blends described above, or At least 30 arrive 90wt%, or at least 40 arrive 90wt%, or at least 50 arrive 90wt%, or at least 60 arrive 90wt%, or at least 70 arrive The dosage of 90wt% is there are polymer (or polyethylene or polypropylene), the weight based on blend interpolymer.

It can be by mixing polymer and one or more of (as described above) polymer of the invention, by connecting together Reactor is connected, manufactures reactor blend, or by, using a kind of catalyst is greater than, producing more in identical reactor Kind polymer species, to produce above-described blend.Polymer can be mixed together before being input in extruder, or Person can in extruder mixed polymer.

Conventional device and method can be used, such as by dry-mixed individual component, and is then melted in mixer mixed It closes, or by mixer, such as this uncle Richter scale mixer, Haake torque rheometer (Haake mixer), Brabender mixing It is directly mixed together each component in machine or single or double screw extruder, forms blend, the extruder may include polymerizeing The compounding extrusion machine and side arm extruder that process downstream directly uses, the polymerization technique may include the hopper in thin film extruding machine Locate the powder or pellet of blending resin.In addition, optionally, it can be in the blend, in one or more of components of blend It is interior, and/or include additive in the product formed by the blend, such as film.This additive is this field many institute's weeks Know, and may include such as filler；Antioxidant (such as Hinered phenols, for example, obtained from Ciba-Geigy IRGANOX1010 or IRGANOX1076)；Phosphite ester (for example, the IRGAFOS168 for being obtained from Ciba-Geigy)；Anti- adhesive additive；Tackifier, example Such as polybutene class, terpene resin, aliphatic series and aromatic hydrocarbon resin, alkali metal and stearine and hydrogenated rosin；UV stablizes Agent；Heat stabilizer；Anti-blocking agent；Remover；Antistatic agent；Pigment；Colorant；Dyestuff；Wax；Silica；Filler；Talcum；With Analog.

Film

In an embodiment according to the present invention, any aforementioned polymer, example can be used in various final applications Such as aforementioned polypropylene class or its blend.Using thin including such as single-layer or multi-layer inflation film, cast film, and/or contraction Film.It can be processed by any amount of well known extrusion or co-extrusion technology, such as the film that froths (blown bubble film) Technology forms these films, wherein circular die can be extruded through composition in the molten state, then expands, and is formed uniaxial Or biaxial orientation melt, it cools down later, forms tubulose inflation film, then can axially cut and the inflation film, shape is unfolded Form flat film.It can be orientated with rear film, uniaxial orientation or biaxial orientation to identical or different degree.Can laterally and/ Or the one or more layers of longitudinal upper oriented film are to identical or different degree.Typical cold drawing or hot-drawn method can be used, it is real Existing uniaxial orientation.Tentering frame equipment or double bubble methods can be used, realize biaxial orientation, and individual layer can be made to be combined together Before or after occur.Be coated or laminated on oriented polypropylene layer for example, polyethylene layer is extrudable, or can by polyethylene and Polypropylene is coextruded into film together, is then orientated.Equally, it can be laminated on the polypropylene to oriented polyethylene of orientation, or orientation Polypropylene can be coated on polypropylene, then optionally or even further be orientated the combination.Typically, on longitudinal direction (MD) with Most 15, or between 5 to 7 ratio, and on transverse direction (TD), with the ratio oriented film of most 15 or 7-9.However, in root According in one embodiment of the invention, oriented film is to identical degree on the two directions MD and TD.

The thickness of film can change, this depends on target application；However, 1-50 μm of film thickness is usually suitable 's.The film for being envisaged for packaging is usually 10-50 μm thick.The thickness of sealant is typically 0.2-50 μm.It can be in the interior table of film There are sealants in face and outer surface the two, or can only there are sealants on inner surface or outer surface.

, can be by sided corona treatment in an embodiment according to the present invention, electron beam irradiation, γ is radiated, at flame Reason or microwave are modified one or more layers.In an embodiment according to the present invention, pass through sided corona treatment modified surface layer One or two layers.

Mold product

Compositions described herein (especially polypropene composition) can also be used in any moulding technology, preparation molding produces Object, wherein moulding technology includes, but are not limited to be molded, the injection molding of air-auxiliary, extrusion blow molded, injection blow molding, injection stretch Blow molding, compression moulding, rotational moulding is foam-formed, thermoforming, sheet extrusion and profile extrusion.Moulding technology is those skilled in the art's public affairs Know.

It further, can be by any suitable way known in the art, by compositions described herein (especially poly- third Ene compositions) it is shaped to the product of required final use.Thermoforming, vacuum forming, blow molding, rotational moulding, slush moulding, die casting, wet-laying Or contact moulding, casting, the matched matched-mold forming of cold forming, injection molding, spraying technology, profile coextrusion or combinations thereof are typically The method used.

Thermoforming is the technique that at least one flexible plastic sheet is formed as required shape.Typically, it is heating The extrudate film of the present composition (and any other layer or material) is placed on shuttle-type frame in the process, to support it.Shuttle Formula frame directs into baking oven, and the baking oven preheated film forms later.Once heating film, then shuttle-type frame is directed to return into In type tool (tool).Then film is vacuumized on shaping jig, holds it in original position, and closed shaping jig.It should Tool keeps closed, to cool down film, then opens the tool.Molding layered product is taken out from the tool.By vacuum, just Hot forming is realized in air pressure, the vacuum forming of piston-auxiliary or these combination and variation, once the sheet material of material reaches Thermoforming temperatures, at typically 140 DEG C -185 DEG C or higher.Using the film bubble step of pre--stretching, especially in big component On, to improve the distribution of material.

Blow molding is another suitable molding mode being used together with composition of the invention, it includes injection blow molding, more Layer blow molding, extrusion blow molded and stretch blow, and particularly suitable for substantially enclosed or hollow object, such as gas tank and its Its fluid container.Blow molding is described more fully in such as CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE In AND ENGINEERING 90-92 (Ja cqueline I.Kroschwitz is edited, John Wiley&Sons1990).

Equally, can by injection molten polymer to mold in, manufacture moulding article, the mold by molten polymer at Type and the required geometry and thickness for hardening into moulding article.Can or it is basic by being squeezed out from die head in chill roll Upper flat profile, or by calendering, manufacture sheet material.Sheet material is generally considered to have 254 μm of -2540 μm of (10mil- Thickness 100mil), but any given sheet material can be significantly thicker.

Supatex fabric and fiber

Above-described polyolefin composition, manufacture can also be used in any supatex fabric and fiber fabrication process Supatex fabric and fiber of the invention, wherein the manufacturing process includes, but are not limited to melt-blown, spunbond, film holed technique (film aperturing) and staple card (staple fiber carding).Continuous filaments technique can also be used.Or Person uses spun-bond process.Spun-bond process is well known in the art.Generally, it involves fiber and is extruded through spinning head.Then using height Fast air stretches these fibers, and layer is layered on annulus.Then, although other technologies can be used, such as ultrasonic bonds and bonding Agent bonding, but usually using stack, heats mesh, and viscose fibre is on each other.

Embodiment

Therefore, the disclosure is related to following embodiment:

E1. the catalyst compounds indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

E2. the catalyst compounds indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

E3. according to the catalyst compounds of embodiment E2, it includes [the O of fac-mer arrangement¹,N,S]-[N,S,O²]。

E4. according to the catalyst compounds of embodiment E2, it includes [the O of mer-fac arrangement¹,N,S]-[N,S,O²]。

E5. according to the catalyst compounds of embodiment E2, it includes [the O of fac-fac arrangement¹,N,S]-[N,S,O²]。

E6. according to the catalyst compounds of any one of embodiment E1-E5, wherein M is Hf or Zr.

E7. according to the catalyst compounds of any one of embodiment E1-E6, wherein X or X1 and X2 is benzyl.

E8. according to the catalyst compounds of any one of embodiment E1-E7, wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It independently is hydrogen, halogen or C₁-C₃₀Alkyl.

E9. according to the catalyst compounds of any one of embodiment E1-E8, wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It independently is hydrogen, halogen or C₁-C₁₀Alkyl.

E10. the catalyst compounds according to any one of embodiment E1-E9 are urged, wherein Y includes o- phenylene two Valence group.

E11. the catalyst compounds indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R^{14 Hes}R¹⁵It independently is hydrogen, C₁-C₄₀Hydrocarbon Base, the functional group of the element of the race containing periodic table of elements 13-17 or two or more R¹-R¹⁵It can connect independently together, Form C₄-C₆₂Cyclic annular or polycyclic ring structure.

E12. the catalyst compounds indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

E13. according to the catalyst compounds of embodiment E12, it includes [the O of fac-mer arrangement¹,N,S]-[N,S, O²]。

E14. according to the catalyst compounds of embodiment E12, it includes [the O of mer-fac arrangement¹,N,S]-[N,S, O²]。

E15. according to the catalyst compounds of embodiment E12, it includes [the O of fac-fac arrangement¹,N,S]-[N,S, O²]。

E16. according to the catalyst compounds of any one of embodiment E12-E15, wherein X¹And X²It is benzyl.

E17. according to the catalyst compounds of any one of embodiment E1-E16, in which:

At least one R², R⁴, R⁵And R⁷Independently selected from: C₁-C₁₀Alkyl, C₁-C₁₀Naphthenic base, C₁-C₁₀Alkenyl C₁-C₁₀Alkane Oxygroup, the C that aryl replaces₁-C₁₀Alkyl, C₁-C₁₀Aryl, halogen group and combinations thereof；With

R¹, R³, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴And R¹⁵It is hydrogen.

E18. according to the catalyst compounds of any one of embodiment E1-E17, wherein at least one R², R⁴, R⁵And R⁷ Independently selected from: methyl, ethyl, isopropyl, isobutyl group, tert-butyl, isopentyl, 2- methyl -2- phenylethyl；Methoxyl group, benzyl Base, adamantyl, chlorine, bromine, iodine and combinations thereof.

E19. according to the catalyst compounds of any one of embodiment E1-E18, in which:

R⁴, R⁵Or combinations thereof be chlorine, bromine, iodine, huge ligand substituting base, or combinations thereof,

Huge ligand substituting base includes the molecular volume that molecular volume is greater than or equal to tert-butyl substituent；With

Huge ligand substituting base includes C₄-C₂₀Alkyl, -- SR^a, -- NR^a ₂, -- PR^a ₂Or combinations thereof, wherein R^aIt is C₄-C₂₀ Alkyl.

E20. according to the catalyst compounds of any one of embodiment E1-E19, wherein R⁴It is containing C₄-C₂₀The Pang of alkyl Big ligand substituting base, and wherein R⁵It is chlorine, bromine or iodine.

E21. according to the catalyst compounds of any one of embodiment E1-E20, wherein R⁴, R⁵Or combinations thereof include carbazole Base or substituted carbazole base.

E22. according to the catalyst compounds of any one of embodiment E1-E21, wherein R⁴Including carbazyl or replace click Oxazolyl, and wherein R⁵It is chlorine, bromine or iodine.

E23. a kind of catalyst system, it includes:

Activator and catalyst compounds according to any one of embodiment E1-E22.

E24. a kind of catalyst system, it includes:

Activator and the catalyst compounds indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

E25. a kind of catalyst system, it includes:

Activator and the catalyst compounds indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

E26. according to the catalyst system of embodiment E25, it includes [the O of fac-mer arrangement¹,N,S]-[N,S,O²]。

E27. according to the catalyst system of embodiment E25, it includes [the O of mer-fac arrangement¹,N,S]-[N,S,O²]。

E28. according to the catalyst system of embodiment E25, it includes [the O of fac-fac arrangement¹,N,S]-[N,S,O²]。

E29. according to the catalyst system of any one of embodiment E23-E28, wherein the activation of catalyst compounds makes [O¹,N,S]-[N,S,O²] it is rearranged to fac-mer arrangement.

E30. according to the catalyst system of any one of embodiment E23-E29, wherein the activation of catalyst compounds makes [O¹,N,S]-[N,S,O²] it is rearranged to fac-fac arrangement.

E31. according to the catalyst system of any one of embodiment E23-E30, wherein activator includes aikyiaiurnirsoxan beta, non-to match Complex anion activator or combinations thereof.

E32. according to the catalyst system of any one of embodiment E23-E31, wherein activator includes aikyiaiurnirsoxan beta, and aluminium Oxygen alkane exists to be greater than or equal to 1mol aluminium/mol catalyst compounds ratio.

E33. according to the catalyst system of any one of embodiment E23-E32, wherein activator is indicated with following formula:

(Z)_d ⁺(A^d-)

Wherein Z is (L-H) or reducible lewis acid, and wherein L is neutral Lewis base, and H is hydrogen；(L-H)⁺For Bronsted acid；

A^d-For the non-coordinating anion with charge d-；With

D is the integer of 1-3.

E34. according to the catalyst system of any one of embodiment E23-E33, wherein activator is indicated with following formula:

(Z)_d ⁺(A^d-)

Wherein A^d-For the non-coordinating anion with charge d-；

D is the integer of 1-3, and

Z is by formula: (Ar₃C⁺) indicate reducible lewis acid, wherein Ar be aryl group, be exchanged for heteroatoms Aryl group, by one or more C₁-C₄₀The aryl group that hydrocarbyl group replaces, is included periodic table of elements 13-17 race The aryl group or their combination that one or more functional groups of element replace.

E35. the method for activated catalyst systems, this method comprises: appointing in conjunction with activator with according to embodiment E1-E22 What one catalyst compounds.

E36. the method for activated catalyst systems, this method comprises: the catalyst indicated in conjunction with activator and with following formula Close object:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

E37. the method for activated catalyst systems, this method comprises: the catalyst indicated in conjunction with activator and with following formula Close object:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein Y is selected from divalent C₁-C₂₀Alkyl, containing the divalent functional groups of the element of 13-17 race in the periodic table of elements and its Combination；With

E38. according to the method for embodiment E37, [the O including fac-mer arrangement¹,N,S]-[N,S,O²]。

E39. according to the method for embodiment E37, [the O including mer-fac arrangement¹,N,S]-[N,S,O²]。

E40. according to the method for embodiment E37, [the O including fac-fac arrangement¹,N,S]-[N,S,O²]。

E41. according to the method for any one of embodiment E36-E40, wherein the activation of catalyst compounds makes [O¹,N, S]-[N,S,O²] it is rearranged to fac-mer arrangement.

E42. according to the method for any one of embodiment E36-E41, wherein the activation of catalyst compounds makes [O¹,N, S]-[N,S,O²] it is rearranged to mer-fac arrangement.

E43. according to the method for any one of embodiment E36-E42, wherein the activation of catalyst compounds makes [O¹,N, S]-[N,S,O²] it is rearranged to fac-fac arrangement.

E44. a kind of method of olefin polymerization, this method include under polymerization conditions, contacting one or more alkene and root According to the catalyst system of any one of embodiment E23-E34, polyolefin is produced.

E45. a kind of method of olefin polymerization, this method:

Under polymerization conditions, one or more alkene and catalyst system are contacted, polyolefin, the catalyst system packet are produced The catalyst compounds for including activator and being indicated with following formula:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

Wherein n is 1 or 2；

E46. a kind of method of olefin polymerization, this method:

Wherein M is the transition metal of the 3rd, 4,5 or 6 race；

E47. a kind of method of olefin polymerization, this method comprises:

Wherein thio-salalen ligand is indicated with following formula:

Wherein metalating agent is indicated with following formula: MX¹X²X³X⁴

Wherein catalyst precarsor is indicated with following formula:

Wherein each solid line in the chemical formula represents covalent bond and each dotted line represents modified covalent degree With the chemical bond of the coordination degree of variation；

Wherein M is the transition metal of the 3rd, 4,5 or 6 race, however condition is the then X in the case where M is trivalent²It is not present；

E48. according to the method for embodiment E46 or E47, [the O including fac-mer arrangement¹,N,S]-[N,S,O²]。

E49. according to the method for embodiment E46 or E47, [the O including mer-fac arrangement¹,N,S]-[N,S,O²]。

E50. according to the method for embodiment E46 or E47, [the O including fac-fac arrangement¹,N,S]-[N,S,O²]。

E51. according to the method for any one of embodiment E44-E50, wherein the activation of catalyst compounds makes [O¹,N, S]-[N,S,O²] it is rearranged to fac-mer arrangement.

E52. according to the method for any one of embodiment E44-E51, wherein the activation of catalyst compounds makes [O¹,N, S]-[N,S,O²] it is rearranged to mer-fac arrangement.

E53. according to the method for any one of embodiment E44-E52, wherein the activation of catalyst compounds makes [O¹,N, S]-[N,S,O²] it is rearranged to fac-fac arrangement.

E54. according to the method for any one of embodiment E44-E53, wherein polymerizing condition includes about 0 DEG C-about 300 DEG C The pressure of temperature, about 0.35MPa- about 10MPa, and about 0.1 minute-about 24 hours time.

E55. according to the method for any one of embodiment E44-E54, one or more of them alkene includes propylene.

E56. according to the method for any one of embodiment E44-E55, wherein polyolefin includes at least 50mol% propylene.

E57. according to the method for any one of embodiment E44-E56, wherein polyolefin have greater than or equal to about Meso isotaxy five unit group [mmmm] concentration of 90wt%, the total weight based on polymer.

E58. according to the method for any one of embodiment E44-E57, wherein existing before in conjunction with activator, and then In the case where there is no separating catalyst compound, when in conjunction with activator, thio-salalen ligand and metalating agent are contacted.

E59. according to the method for any one of embodiment E44-E58, wherein in the presence of an activator, one or more In the presence of alkene, or a combination thereof under, contact thio-salalen ligand and metalating agent.

E60. the method for preparing thio-salalen catalyst compounds, this method comprises:

Use chemical formula MX¹X²X³X⁴The metalating agent of expression and the thio-salalen ligand reaction indicated with following formula:

Wherein every X¹, X², X³And X⁴It independently is monovalent C₁-C₂₀Alkyl, the member containing 13-17 race in the periodic table of elements The functional group of element or X¹And X²(if present) it connects together, forms C₄-C₆₂Cyclic annular or polycyclic ring structure；

E61. the method for embodiment E60 further comprises making amineothiot NH₂- Y-SH, halogenated-methylphenol and water Poplar aldehyde reaction forms thio-salalen ligand.

E62. the method for embodiment E61, including make amineothiot NH₂- Y-SH is reacted with halogenated-methylphenol, is formed Amino-is thio-methylphenol, and make amino-it is thio-methylphenol and bigcatkin willow aldehyde reaction.

E63. the method for embodiment E61, including make amineothiot NH₂- Y-SH and bigcatkin willow aldehyde reaction form mercaptan imido Base phenol, and make halogenated-methylphenol and mercaptan imino group phenol reactant.

E64. according to the method for any one of embodiment E61-E63, wherein salicylide is by R¹, R², R³, R⁴And R¹¹Replace.

E65. according to the method for any one of embodiment E61-E64, wherein halogenated-methylphenol is by R⁵, R⁶, R⁷, R⁸, R⁹ And R¹⁰Replace.

E66. according to the method for any one of embodiment E61-E65, wherein R⁴, R⁵Or combinations thereof include carbazyl or taking For carbazyl.

E67. according to the method for any one of embodiment E61-E66, wherein R⁴, R⁵Or combinations thereof include 3,6- bis--tertiary fourth Base carbazole -9- base.

Embodiment

Experiment

It can refer to following non-limiting embodiments, the discussion before further describing.Under room temperature (25 DEG C), purifying Nitrogen atmosphere under, using the glove box of standard, high vacuum or Schlenk technology carry out all reactions, unless otherwise indicated.Institute The solvent used be it is anhydrous, what the sum of deoxidation was purified according to known process.All starting materials purchased from Aldrich and It purifies or is prepared according to process well known by persons skilled in the art before the use.

Eight illustrative catalyst compounds (A to H), wherein respectively implementing according to the one or more are synthesized Scheme:

Example A:

M=Hf, Zr, Ti

Example B:

M=Hf, Zr, Ti

Example C:

M=Hf, Zr, Ti

Example D:

M=Hf, Zr, Ti

Example E:

M=Hf, Zr, Ti

Example F:

M=Hf, Zr, Ti

Example G:

M=Hf, Zr, Ti

Example H

M=Hf, Zr, Ti

Example I (ligand)

Example J (ligand)

Synthesize 2- ((2- aminothiophene base) methyl) -4,6- chlorophenesic acid.By 2- (bromomethyl) -4,6- chlorophenesic acid The solution of (1.24g, 4.8mmol) in THF (20mL) is added dropwise to 2- aminothiophenol (0.60g, 4.8mmol) and three second Amine (0.70mL) is stirred at room temperature 12 hours in the solution in THF (20mL).Solid is formd, and is filtered, then very Sky removes solvent.In methylene chloride by crude product dissolution, it is washed with saturation NaCl solution, and in MgSO₄Upper drying.With quantitative Yield obtain yellow oil form product.

¹H NMR(400MHz,CDCl₃),δ7.21-7.09(m,3H,ArH),6.78-6.59(m,3H,ArH),4.44 (brs,2H,ArNH₂),3.90(s,2H,ArCH₂S)。

Synthesize 2- ((2- aminothiophene base) methyl) -4,6- dibromophenol.By 2- (bromomethyl) -4,6- dibromophenol The solution of (1.48g, 4.3mmol) in THF (20mL) is added dropwise to 2- aminothiophenol (0.54g, 4.3mmol) and three second Amine (0.60mL) is stirred at room temperature 12 hours in the solution in THF (20mL).Solid is formd, and is filtered, then very Sky removes solvent.In methylene chloride by crude product dissolution, it is washed with saturation NaCl solution, and in MgSO₄Upper drying.With quantitative Yield obtain yellow oil form product.

¹H NMR(400MHz,CDCl₃), δ 7.46 (d, 1H, J=4.8Hz, ArH), 7.20-7.09 (m, 2H, ArH), 6.92 (d, 1H, J=4.8Hz, ArH), 6.76-6.60 (m, 2H, ArH), 4.24 (brs, 2H, ArNH₂),3.90(s,2H,ArCH₂S)。

Synthesize 2- ((2- aminothiophene base) methyl) -4,6- DI-tert-butylphenol compounds.By 2- (bromomethyl) -4,6- di-t-butyl Solution of the phenol (1.03g, 3.4mmol) in THF (20mL) be added dropwise to 2- aminothiophenol (0.43g, 3.4mmol) and Triethylamine (0.50mL) is stirred at room temperature 12 hours in the solution in THF (20mL).Solid is formd, and is filtered, is connect Solvent is removed in vacuum.In methylene chloride by crude product dissolution, it is washed with saturation NaCl solution, and in MgSO₄Upper drying.With Quantitative yield obtains the product of yellow oil form.

¹H NMR(400MHz,CDCl₃), δ 7.24 (d, 1H, J=2.0Hz, ArH), 7.13-7.03 (m, 2H, ArH), 6.74-6.52(m,3H,ArH),4.31(brs,2H,ArNH₂),3.95(s,2H,ArCH₂S),1.37(s,9H,C(CH₃)₃), 1.16(s,9H,C(CH₃)₃)。

Synthesize 2- ((2- aminothiophene base) methyl) -4- methyl -6- adamantyl phenol.By 2- (bromomethyl) -4,6- two Solution of the tert-butyl phenol (1.00g, 3.0mmol) in THF (20mL) be added dropwise to 2- aminothiophenol (0.37g, 3.0mmol) and triethylamine (0.41mL) is in the solution in THF (20mL), and is stirred at room temperature 12 hours.It forms solid Body, and filter, solvent is then removed in vacuum.In methylene chloride by crude product dissolution, it is washed with saturation NaCl solution, and MgSO₄Upper drying.Product in the form of quantitative yield obtains yellow oil.

¹H NMR(400MHz,CDCl₃), δ 7.21-7.08 (m, 2H, ArH), 6.89 (d, 1H, J=2.0Hz, ArH), 6.73-6.69 (m, 1H, ArH), 6.65 (d, 1H, J=2.0Hz, ArH), 6.63-6.58 (m, 1H, ArH), 4.33 (brs, 2H, ArNH₂),3.94(s,2H,ArCH₂S),2.17(s,3H,ArCH₃), 2.10 (m, 3H, adamantyls), 2.06 (m, 6H, adamantane Base), 1.77 (m, 6H, adamantyls).

Synthesize 2- ((2- mercaptophenyl imino group) methyl) -4,6- DI-tert-butylphenol compounds.It, will in closed glass container Solution of the 3,5- di-t-butyl -2- hydroxyl benzyl aldehyde (6.79g, 0.03mol) in benzene (50mL) is added dropwise to 2- aminobenzene sulphur Phenol (3.63g, 0.03mol) heats 3 days in the solution in benzene (50mL), and at 100 DEG C.Solvent is removed in vacuum.With quantitative Yield obtain yellow oil form product.

¹H NMR(200MHz,CDCl₃),δ7.91-7.86(m,2H,ArH),7.55-7.38(m,5H,ArH),1.50(s, 9H,C(CH₃)₃),1.36(s,9H,C(CH₃)₃)。

Synthesize example A-H₂.By 2- ((2- aminothiophene base) methyl) -4,6- chlorophenesic acid (0.42g, 1.4mmol) in second Solution in alcohol (20mL) is added to solution of the bis- chlorine-2-hydroxyl benzyl aldehyde (0.26g, 1.4mmol) of 3,5- in ethyl alcohol (20mL) In, and be stirred at room temperature 2 hours.Solvent is evaporated, orange solids are obtained with 99% ultimate yield.

¹H NMR(500MHz,CDCl₃),δ8.41(s,1H,NCH),7.44(m,2H,ArH),7.33-7.27(m,3H, ), ArH 7.18 (d, 1H, J=10.7Hz, ArH), 7.12 (d, 1H, J=2.4Hz, ArH), 6.87 (d, 1H, J=2.4Hz, ArH),4.06(s,2H,ArCH₂S)；¹³C NMR(125MHz,CDCl₃),δ159.0(CN),156.3(C),148.6(C), 147.2(C),133.4(CH),131.8(CH),131.7(C),130.3(CH),129.0(CH),128.7(CH),127.7 (CH),127.2(CH),126.7(C),125.3(C),123.7(C),123.4(C),121.1(C),120.5(C),118.0 (CH),33.5(CH₂)。

It synthesizes example A Zr (O-tert-Bu)₂.By example A-H₂(37mg, 0.08mmol) is dissolved in 2mL ether, and in room Under temperature, it is added dropwise to Zr (O^tBu)₄₍30mg, 0.08mmol) solution in.Stir the solution 2 hours, vacuum is removed later Solvent is removed, orange solids (49mg, 70%) is obtained.

¹H NMR(400MHz,C₆D₆), product 1: δ 7.40 (d, 1H, J=2.6Hz, ArH), 7.13 (s, 1H, NCH), 7.00 (d, 1H, J=4.4Hz, ArH), 6.65 (d, J=2.6,1H, ArH), 6.62-6.51 (m, 4H, ArH), 4.36 (bs, 1H, CH₂),3.35(bs,1H,CH₂),1.37(bs,9H,C(CH₃)₃),1.27(bs,9H,C(CH₃)₃) product 2: δ 7.44 (s, 2H, ), NCH 7.37 (m, 2H, ArH), 7.26 (d, 2H, J=2.6Hz, ArH), 7.04 (d, 2H, J=2.4Hz, ArH), 6.88 (m, 4H, ArH), 6.65 (m, 2H, ArH), 6.33 (m, 4H, ArH), 3.88 (d, 2H, J=13.7Hz, CH₂), 3.36 (d, J= 13.8,2H,CH₂)；¹³C NMR(100.66MHz,C₆D₆), product 1: δ 167.8 (CN), 160.7 (C), 158.4 (C), 139.1 (C),138.6(C),129.7(CH),129.6(CH),128.5(CH),128.1(CH),124.9(C),123.4(C),122.1 (C),119.8(C),59.2(CH₂),35.5(CH₂),34.5(CH₂),33.9(C),32.5(CH₃),31.3(CH₃),31.1(C), 29.7(CH₃) product 2: δ 134.7 (CN), 159.1 (C), 158.1 (C), 156.5 (C), 140.8 (CH), 137.4 (CH), 135.6(CH),131.2(CH),129.2(CH),128.9(CH),128.8(CH),128.5(CH),125.6(C),125.5 (C),124.9(C),124.1(C),122.0(CH),121.4(C),115.6(C),109.0(C),65.9(CH₂).For C₃₂H₄₇Cl₂NO₄The analytical calculation of SZr: C, 54.60；H,6.73；N,1.99.It was found that: C, 53.82；H,6.43；N,1.75.

Synthesize Example C-H₂.By 2- ((2- aminothiophene base) methyl) -4,6- DI-tert-butylphenol compounds (1.00g, 2.9mmol) solution in ethyl alcohol (20mL) is added to bis- chlorine-2-hydroxyl benzyl aldehyde (0.55g, 2.9mmol) of 3,5- in ethyl alcohol In solution in (20mL), and it is stirred at room temperature 2 hours.Solvent is evaporated, and by flash chromatography, in Silica gel Use the increased petroleum ether of polarity on 60: the mixture of methylene chloride is as eluant, eluent, purification of crude product.With 69% final production Rate, by orange to obtaining pure products in the form of red solid.

¹H NMR(500MHz,CDCl₃), δ 8.50 (s, 1H, NCH), 7.47 (s, 1H, ArH), 7.42 (d, 1H, J= 7.6Hz,ArH),7.31-7.28(m,2H,ArH),7.25-7.21(m,2H,ArH),7.18-7.16(m,2H,ArH),4.12 (s,2H,ArCH₂S),1.37(s,9H,C(CH₃)₃),1.20(s,9H,C(CH₃)₃)；¹³C NMR(125MHz,CDCl₃),δ160.5 (CN),156.4(C),151.5(C),147.3(C),142.7(C),137.3(CH),133.3(CH),132.3(CH),130.8 (C),130.3(C),130.1(CH),128.7(CH),128.4(CH),125.5(CH),124.1(CH),123.6(C),121.8 (C),120.5(C),118.1(CH),36.5(CH₂),35.1(C),34.4(C),31.7(CH₃),30.0(CH₃)。

Synthesize example D-H₂.By 2- ((2- aminothiophene base) methyl) -4,6- chlorophenesic acid (0.82g, 2.7mmol) in benzene Solution in (20mL) is added to 3- adamantyl -2- hydroxy-5-methyl base benzyl aldehyde (0.74g, 2.7mmol) in benzene (20mL) In solution and flow back 5 hours.Solvent is evaporated, and by flash chromatography, the increased petroleum of polarity is used on Silica gel 60 Ether: the mixture of methylene chloride is as eluant, eluent, purification of crude product.With 50% ultimate yield, obtained in the form of orange solids Pure products.

¹H NMR(500MHz,CDCl₃), δ 8.47 (s, 1H, NCH), 7.41 (dd, 1H, J=7.7,1.4Hz, ArH), 7.33-7.30 (m, 1H, ArH), 7.23-7.21 (m, 1H, ArH), 7.18 (d, 2H, J=2.44Hz, ArH), 7.13 (dd, 1H, J =7.7,1.4Hz, ArH), 7.04 (s, 1H, ArH), 6.99 (d, 1H, J=2.44Hz, ArH), 4.09 (s, 2H, ArCH₂S), 2.33(s,3H,ArCH₃)2.24(m,5H,Ad),2.13(m,3H,Ad),1.81(m,7H,Ad)；¹³C NMR(125MHz, CDCl₃),δ163.9(CN),159.0(C),156.5(C),133.3(C),132.5(C),132.2(C),131.7(C),130.8 (CH),130.0(C),129.1(C),128.9(C),128.8(C),128.6(CH),128.5(CH),127.7(CH),127.2 (CH),118.6(CH),118.2(CH),40.9(CH₂),40.5(CH₂),37.4(CH₃),37.3(CH₂),33.3(C),29.3 (CH₂)。

It synthesizes example D Hf (Bn)₂.By example D-H₂(48mg, 0.09mmol) is dissolved in 2mL cold toluene, and by its by It is added dropwise to Hf (Bn)₄₍47mg, 0.09mmol) in solution in toluene.It stirs the solution 2 hours, is removed in vacuum later molten Agent, and obtained solid is washed with pentane, obtain quantitative yield.

It synthesizes example D Zr (O-tert-Bu)₂.By example D-H₂(35mg, 0.06mmol) is dissolved in 2mL ether, and in room Under temperature, it is added dropwise to Zr (O^tBu)₄₍24mg, 0.06mmol) solution in.Stir the solution 2 hours, vacuum is removed later Solvent is removed, yellow is obtained to orange solids (53mg) with quantitative yield.

¹H NMR(400MHz,C₆D₆),δ7.82(s,1H,NCH),7.39(s,1H,ArH),7.14(s,1H,ArH),7.08 (s, 1H, ArH), 6.86 (t, 1H, J=7.4Hz, ArH), 6.80 (t, 1H, J=6.9, ArH), 6.72 (s, 1H, ArH), 6.54 (d, 1H, J=7.7, ArH), 3.91 (d, 1H, J=13.1, CH₂), 3.33 (d, 1H, J=12.7, CH₂),2.57(m,7H,Ad), 2.31(m,5H,Ad),2.11(m,3H,Ad),1.96(m,4H,Ad),1.62(s,9H,C(CH₃)₃),1.18(s,9H,C (CH₃)₃)；¹³C NMR(100.66MHz,C₆D₆),δ166.7(CN),162.4(C),161.1(C),159.5(C),154.1(C), 139.9(C),136.1(CH),134.3(CH),131.8(CH),129.7(CH),127.4(CH),126.8(C),124.7(C), 124.5(C),123.9(C),123.2(C),120.0(CH),75.6(C),72.7(C),40.9(CH₂),40.8(Ad),37.6 (CH₃),33.1(Ad),32.4(CH₃),31.3(Ad),29.7(Ad)。

Synthesize example F-H₂.By 2- ((2- aminothiophene base) methyl) -4- methyl -6- adamantyl phenol (1.00g, 2.6mmol) solution in ethyl alcohol (20mL) is added to bis- chlorine-2-hydroxyl benzyl aldehyde (0.50g, 2.6mmol) of 3,5- in ethyl alcohol In solution in (20mL), and it is stirred at room temperature 2 hours.Solvent is evaporated, and by flash chromatography, in Silica gel Use the increased petroleum ether of polarity on 60: the mixture of methylene chloride is as eluant, eluent, purification of crude product.With 55% final production Rate obtains pure products in the form of orange solids.

¹H NMR(500MHz,CDCl₃),δ8.45(s,1H,NCH),7.50-7.47(m,2H,ArH),7.33-7.25(m, 2H, ArH), 7.17 (d, 1H, J=7.7Hz, ArH), 6.89 (s, 1H, ArH), 6.63 (s, 1H, ArH), 5.86 (s, 1H, ArH), 4.07(s,2H,ArCH₂S),2.15(s,3H,ArCH₃),2.05(m,9H,Ad),1.75(m,6H,Ad)；¹³C NMR(125MHz, CDCl₃),δ161.1(CN),156.5(C),151.9(C),147.4(C),138.2(C),133.3(CH),132.5(CH), 130.8(C),130.0(CH),129.6(C),128.9(CH),128.8(CH),128.5(CH),127.7(CH),123.6(C), 122.7(C),120.4(C),118.2(CH),118.1(C),40.9(CH₂),37.3(CH₂),37.1(C),36.4(CH₃), 29.3(CH),20.9(CH₂)。

It synthesizes example F Hf (Bn)₂.By example F-H₂(61mg, 0.11mmol) is dissolved in 2mL cold toluene, and by its by It is added dropwise to Hf (Bn)₄₍60mg, 0.06mmol) in solution in toluene.It stirs the solution 2 hours, is removed in vacuum later molten Agent, and obtained solid is washed with pentane, obtain quantitative yield.

¹H NMR(400MHz,C₆D₆), δ 7.29 (d, 1H, J=2.6Hz, ArH), 7.24 (s, 1H, NCH), 7.15-6.88 (m, 14H, ArH), 6.83 (d, 1H, J=1.5Hz, ArH), 6.39 (d, 1H, J=2.6Hz, ArH) 6.21 (d, 1H, J= 1.5Hz, ArH), 3.90 (d, 1H, J=13.8Hz, CH₂), 3.57 (d, J=13.8,1H, CH₂), 2.73 (d, 1H, J= 10.0Hz,CH₂), 2.57 (d, J=10.7,1H, CH₂), 2.48 (d, J=10.0,1H, CH₂),2.06(s,3H,CH₃)；1.99- 1.75 (m, 15H, adamantyls)；

It synthesizes example F Zr (Bn)₂.By example F-H₂(53mg, 0.10mmol) is dissolved in 2mL cold toluene, and by its by It is added dropwise to Zr (Bn)₄₍44mg, 0.09mmol) in solution in toluene.It stirs the solution 2 hours, is removed in vacuum later molten Agent, and obtained solid is washed with pentane, obtain quantitative yield.

¹H NMR(400MHz,C₆D₆), δ 7.30 (d, 1H, J=2.7Hz, ArH), 7.19 (s, 1H, NCH), 7.12-6.82 (m, 16H, ArH), 6.25 (d, 1H, J=1.1Hz, ArH), 4.26 (d, 1H, J=13.7Hz, CH₂), 3.62 (d, J=13.7, 1H,CH₂), 2.88 (d, 1H, J=8.3Hz, CH₂), 2.59 (d, J=8.3,1H, CH₂), 2.20 (d, J=9.5,1H, CH₂), 2.06(s,3H,CH₃), 1.94-1.58 (m, 15H, adamantyl)；

Synthesize example G-H₂.By 2- ((2- aminothiophene base) methyl) -4,6- dibromophenol (1.35g, 3.5mmol) in second Solution in alcohol (20mL) is added to solution of the bromo- 2- hydroxyl benzyl aldehyde (0.97g, 3.5mmol) of 3,5- bis- in ethyl alcohol (20mL) In, and be stirred at room temperature 7 hours.Solvent is evaporated, and by flash chromatography, is increased on Silica gel 60 with polarity Petroleum ether: the mixture of methylene chloride is as eluant, eluent, purification of crude product.With 35% ultimate yield, with red solid shape Formula obtains pure products.

¹H NMR(500MHz,CDCl₃), δ 8.35 (s, 1H, NCH), 7.73 (d, 1H, J=1.7Hz, ArH), 7.46-7.43 (m, 2H, ArH), 7.36-7.32 (m, 2H, ArH), 7.27 (d, 1H, J=10.1Hz, ArH), 7.16 (d, 1H, J=13.8Hz, ), ArH 6.96 (d, 1H, J=1.3Hz, ArH), 4.03 (s, 2H, ArCH₂S)；¹³C NMR(125MHz,CDCl₃),δ159.8 (CN),157.6(C),149.8(C),147.3(C),138.6(CH),133.7(CH),133.2(CH),132.5(CH),132.4 (CH),131.5(C),128.8(CH),128.7(CH),127.1(C),121.1(C),118.1(CH),112.8(C),112.5 (C),111.5(C),110.5(C),34.0(CH₂)。

Synthesize example H-H₂.By 2- ((2- aminothiophene base) methyl) -4,6- chlorophenesic acid (0.60g, 2.0mmol) in benzene Solution in (20mL) is added to solution of the 3,5- di-t-butyl -2- hydroxyl benzyl aldehyde (0.15g, 2.0mmol) in benzene (20mL) In, and flow back 5 hours.Solvent is evaporated, and by flash chromatography, the increased petroleum ether of polarity is used on Silica gel 60: The mixture of methylene chloride is as eluant, eluent, purification of crude product.With 71% ultimate yield, pure production is obtained in the form of orange solids Object.

Alternative synthesis example H-H₂.By 2- (bromomethyl) -4,6- chlorophenesic acid (1.12g, 4.4mmol) in THF Solution in (20mL) be added dropwise to 2- ((2- mercaptophenyl imino group) methyl) -4,6- DI-tert-butylphenol compounds (1.50g, 4.4mmol) and triethylamine (3mL) is in the solution in THF (20mL), and is stirred at room temperature 2 hours.Solid is formd, and Filtering, is then removed in vacuum solvent.In methylene chloride by crude product dissolution, it is washed and with saturation NaCl solution in MgSO₄On It is dry.Product in the form of quantitative yield obtains orange solids.

¹H NMR(500MHz,CDCl₃), δ 8.42 (s, 1H, NCH), 7.46 (s, 1H, ArH), 7.39 (d, 1H, J= 7.6Hz,ArH),7.30(m,1H,ArH),7.19(m,2H,ArH),7.14-7.12(m,1H,ArH),6.94(s,1H,ArH), 4.06(s,2H,ArCH₂S),1.49(s,9H,C(CH₃)₃),1.33(s,9H,C(CH₃)₃)；¹³C NMR(125MHz,CDCl₃),δ 164.0(CN),158.6(C),149.4(C),148.5(C),140.8(C),137.4(C),132.1(C),131.7(CH), 130.4(C),129.1(CH),128.6(CH),128.5(CH),128.1(C),127.7(CH),127.3(CH),127.2 (CH),126.8(C),125.2(C),118.6(CH),33.3(CH₂),31.7(CH₃),31.5(C),29.7(CH₃),29.5 (C)。

It synthesizes example H Zr (O-tert-Bu)₂.By example H-H₂(44mg, 0.09mmol) is dissolved in 2mL ether, and in room Under temperature, it is added dropwise to Zr (O^tBu)₄₍33mg, 0.09mmol) solution in.Stir the solution 2 hours, vacuum is removed later Solvent is removed, yellow solid (64mg) is obtained with quantitative yield.

¹H NMR(400MHz,C₆D₆),δ7.79(s,1H,NCH),7.75(s,1H,ArH),7.09(s,1H,ArH),7.02 (m, 2H, ArH), 6.73 (t, 1H, J=7.5Hz, ArH), 6.68 (t, 1H, J=7.2Hz, ArH), 6.35 (m, 2H, ArH), 3.91 (d, 1H, J=12.0, CH₂), 3.27 (d, 1H, J=12.9, CH₂),1.77(s,9H,C(CH₃)₃),1.51(bs,9H,C (CH₃)₃),1.34(s,9H,C(CH₃)₃),1.12(bs,9H,C(CH₃)₃)；¹³C NMR(100.66MHz,C₆D₆),δ167.3 (CN),162.2(C),159.1(C),154.1(C),140.2(C),139.4(C),136.0(CH),132.0(CH),131.6 (CH),130.7(CH),129.7(CH),127.1(CH),124.7(C),123.8(C),123.7(C),123.3(C),120.0 (CH),119.4(C),40.4(CH₂),33.3(CH₃),32.5(CH₃),31.6(CH₃),31.5(C),31.1(C),30.0 (CH₃)。

Synthesize example I ligand.According to following reaction equations, preparating example I ligand:

Synthesize example J ligand.According to following reaction equations, preparating example J ligand:

Remaining example is consistently synthesized with above-mentioned synthesis.

The molecular structure measured by the Advances in crystal X-ray diffraction of embodiment A, C and G is respectively as shown in Fig. 1,2 and 3.

Fig. 1 is shown according to the following formula, according to the X-ray crystal structure of the thio-salalen catalyst of embodiment A, Middle metal is Zr:

Structure is shown in Fig. 1, wherein for the sake of clarity, eliminating the tert-butyl in each tert-butoxy.

Fig. 2 shows according to the following formula, according to the X-ray crystal structure of the thio-salalen catalyst of embodiment C, Middle metal is Zr, and wherein benzyl is substituted by O-t-Bu:

Structure is shown in Fig. 2, wherein for the sake of clarity, eliminating the tert-butyl in each tert-butoxy.

Fig. 3 is shown according to the following formula, according to the X-ray crystal structure of the thio-salalen catalyst of embodiment G, Middle metal is Zr, and wherein benzyl is substituted by O-t-Bu:

Structure is shown in Fig. 3, wherein for the sake of clarity, eliminating the tert-butyl in each tert-butoxy.

As shown in these figures, thio-salalen ligand according to embodiments of the present invention produces fac-fac package Structure.

Use three illustrative polymerizing olefins with catalyst.Under room temperature (25 DEG C), using example D, it polymerize pure C alkene 13 Hour, wherein M=Hf.These data have been shown in table 1.

Table 1

Under similar conditions, using different metal, a series of pure propylene polymerization is carried out.These numbers have been shown in table 2 According to.

Table 2

Under conditions of substantially the same with upper table 1, pure 1- hexene is polymerize at 25 DEG C.It has been shown in table 3 these numbers According to.

Table 3

Therefore, it will be seen that the halogen group on the ortho position of bulky group and thio side phenol on the ortho position of imines side phenol Combination seem to cause the isotactic polymer of height.

With zirconium as example J ligand is used in the catalyst of metal and benzyl reactive group, using MAO and Trityl-D4 is as activator, olefin polymerization.Result is listed in table 4.

Table 4

Just as can be seen from this data, catalyst compounds disclosed herein, catalyst system and polymerization provide novel And improved catalyst and system, for olefinic polymerization, this, which will be generated, has the polymer for improving performance, such as high polymer Fusing point and high isotachyte.

Catalyst in the present embodiment provides the improvement of catalyst activity, and generating has the polymerization for improving performance Object, or both.In an embodiment according to the present invention, crystallographic techniques show additional one or more ring bodies System is the fac-fac of orientation.In an embodiment according to the present invention, the structure of these catalyst is during polymerization technique The wide channel of polymer moieties is provided to be resident and monomer insertion.Just because of this, the embodiment of disclosure according to the present invention Catalyst provide control polymerization, steric regularity, comonomer insertion etc. one or more features ability.

All documents as described herein are herein by reference in introducing, including any priority documents and/or survey Trial work sequence, degree make they not with conflict herein, however, condition be do not mentioned in the application initially submitted it is any Priority documents or the document of submission are not incorporated by reference into herein.According to aforementioned general remark and specific embodiment, It is readily apparent that although illustrating and describing various forms of the invention spirit and model of the invention can be detached from no Various modifications are made in the case where enclosing.Therefore, it is not intended to limit the present invention so far.

Claims

1. the catalyst compounds indicated with following formula:

Wherein each solid line represents covalent bond and each dotted line represents modified covalent degree and the coordination degree of variation Chemical bond；

Wherein M is Hf, Zr or Ti；

Wherein n is 2；

Wherein every X independently is monovalent C₁-C₂₀Alkyl, halogen, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are suitable whole Number is to provide electroneutral part；

Wherein Y is selected from divalent C₃-C₂₀Alkyl, divalent C₃-C₂₀Alkyl, it includes halogen, O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein each R* is independently C₁-C₂₀ Alkyl and wherein x are suitable integers to provide electroneutral part, and combinations thereof；With

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It independently is hydrogen, C₁-C₁₀Alkyl, halogen, O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein often A R* is independently C₁-C₂₀Alkyl and wherein x are suitable integers to provide electroneutral part or two or more R¹- R¹¹It can be independently connected together, form C₄-C₆₂Cricoid ring structure.

2. the catalyst compounds indicated with following formula:

Wherein M is Hf, Zr or Ti；

Wherein every X¹And X²It independently is monovalent C₁-C₂₀Alkyl, halogen, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are to close Suitable integer is to provide electroneutral part or X¹And X²It links together, forms C₄-C₆₂Cricoid ring structure；

3. catalyst compounds according to claim 2, it has [the O of fac-mer arrangement¹,N,S]-[N,S,O²]。

4. catalyst compounds according to claim 2, it has [the O of mer-fac arrangement¹,N,S]-[N,S,O²]。

5. catalyst compounds according to claim 2, it has [the O of fac-fac arrangement¹,N,S]-[N,S,O²]。

6. the catalyst compounds of -5 any one according to claim 1, wherein M is Hf or Zr.

7. the catalyst compounds of -5 any one according to claim 1, wherein X or X¹And X²It is benzyl.

8. the catalyst compounds of -5 any one according to claim 1, wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It independently is hydrogen, halogen or C₁-C₁₀Alkyl.

9. the catalyst compounds of -5 any one according to claim 1, wherein Y is o- phenylene bivalent group.

10. the catalyst compounds indicated with following formula:

Wherein M is Hf, Zr or Ti；

Wherein n is 2；

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴And R¹⁵It independently is hydrogen, C₁-C₁₀Alkyl, Halogen, O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are suitable integers to provide electroneutral part or two Or more R¹-R¹⁵It can be independently connected together, form C₄-C₆₂Cricoid ring structure.

11. the catalyst compounds indicated with following formula:

Wherein M is Hf, Zr or Ti；

Wherein every X¹And X²It independently is monovalent C₁-C₂₀Alkyl, halogen, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are to close Suitable integer is to provide electroneutral part；With

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴And R¹⁵It independently is hydrogen, C₁-C₁₀Alkyl, Halogen, O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are suitable integers to provide electroneutral part or two Or more R¹-R¹⁵It can be independently connected together, form C₄-C₆₂Cricoid ring structure.

12. catalyst compounds according to claim 11, it has [the O of fac-mer arrangement¹,N,S]-[N,S,O²]。

13. catalyst compounds according to claim 11, it has [the O of mer-fac arrangement¹,N,S]-[N,S,O²]。

14. catalyst compounds according to claim 11, it has [the O of fac-fac arrangement¹,N,S]-[N,S,O²]。

15. the catalyst compounds of any one of 1-14 according to claim 1, wherein each X_n, if it exists, or X¹With X², if it exists, being benzyl.

16. the catalyst compounds of any one of 1-14 according to claim 1, in which:

R², R⁴, R⁵And R⁷At least one of independently selected from C₁-C₁₀Alkyl, C₁-C₁₀Naphthenic base, C₁-C₁₀Alkenyl, C₁-C₁₀Alkane Oxygroup, C₁-C₁₀The C that aryl replaces₁-C₁₀Alkyl, C₁-C₁₀Aryl, halogen group and combinations thereof；With

17. the catalyst compounds of any one of 1-14 according to claim 1, wherein R², R⁴, R⁵And R⁷At least one of it is independent Ground is selected from: methyl, ethyl, isopropyl, isobutyl group, tert-butyl, isopentyl, 2- methyl -2- phenylethyl；Methoxyl group, benzyl, gold Rigid alkyl, chlorine, bromine, iodine and combinations thereof.

18. the catalyst compounds of any one of 1-14 according to claim 1, in which:

R⁴, R⁵Or combinations thereof be chlorine, bromine, iodine, huge ligand substituting base or combinations thereof, wherein huge ligand substituting base is point Sub-volume is greater than or equal to the substituent group of the molecular volume of tert-butyl substituent.

19. catalyst compounds according to claim 18, wherein huge ligand substituting base is C₄-C₁₀Alkyl ,-SR^a,-NR^a ₂ Or-PR^a ₂, wherein R^aIt is C₄-C₂₀Alkyl.

20. catalyst compounds according to claim 18, wherein R⁴It is huge ligand substituting base, and wherein R⁵Chlorine, bromine or Iodine.

21. the catalyst compounds of any one of 1-14 according to claim 1, wherein R⁴, R⁵Or combinations thereof be carbazyl.

22. the catalyst compounds of any one of 1-14 according to claim 1, wherein R⁴It is carbazyl, and wherein R⁵It is chlorine, bromine Or iodine.

23. a kind of catalyst system, it includes:

Activator and the according to claim 1 catalyst compounds of any one of -5 or 11-14.

24. a kind of catalyst system, it includes:

Activator and the catalyst compounds indicated with following formula:

Wherein M is Hf, Zr or Ti；

Wherein n is 2；

25. a kind of catalyst system, it includes:

Activator and the catalyst compounds indicated with following formula:

Wherein M is Hf, Zr or Ti；

26. catalyst system according to claim 25, it has [the O of fac-mer arrangement¹,N,S]-[N,S,O²]。

27. catalyst system according to claim 25, it has [the O of mer-fac arrangement¹,N,S]-[N,S,O²]。

28. catalyst system according to claim 25, it has [the O of fac-fac arrangement¹,N,S]-[N,S,O²]。

29. wherein the activation of catalyst compounds makes [O according to the catalyst system of any one of claim 24-28¹,N,S]- [N,S,O²] it is rearranged to fac-mer arrangement.

30. wherein the activation of catalyst compounds makes [O according to the catalyst system of any one of claim 24-28¹,N,S]- [N,S,O²] it is rearranged to fac-fac arrangement.

31. wherein activator is aikyiaiurnirsoxan beta, non-coordinating anion according to the catalyst system of any one of claim 24-28 Activator or combinations thereof.

32. wherein activator is aikyiaiurnirsoxan beta, and aikyiaiurnirsoxan beta is with big according to the catalyst system of any one of claim 24-28 In or equal to the presence of 1mol aluminium/mol catalyst compounds ratio.

33. wherein activator is indicated with following formula according to the catalyst system of any one of claim 24-28:

(Z)_d ⁺(A^d-)

Wherein Z is (L-H) or reducible lewis acid, and wherein L is neutral Lewis base, and H is hydrogen；(L-H)⁺For Bu Langsi Platform moral acid；

A^d-For the non-coordinating anion with charge d-；With

D is the integer of 1-3.

34. wherein activator is indicated with following formula according to the catalyst system of any one of claim 24-28:

(Z)_d ⁺(A^d-)

Wherein A^d-For the non-coordinating anion with charge d-；

D is the integer of 1-3, and

Z is by formula: (Ar₃C⁺) indicate reducible lewis acid, wherein Ar be the aryl group with 3-20 carbon atom, The aryl group with 3-20 carbon atom being exchanged for heteroatoms, by one or more C₁-C₄₀What hydrocarbyl group replaced has The aryl group of 3-20 carbon atom includes halogen, O, S, Se, Te, NR*_x、OR*、SeR*、TeR*、PR*_x、AsR*_x、SbR*_x、 SR*、BR*_x、SiR*_x、GeR*_x、SnR*_x、PbR*_xOr combinations thereof the aryl group with 3-20 carbon atom, wherein each R* It is independently C₁-C₂₀Alkyl and wherein x are suitable integers to provide electroneutral part or their combination.

35. the method for activated catalyst systems, this method comprises: in conjunction with activator and according to claim 1-5,10-14 or 24- The catalyst compounds of 28 any one.

36. the method for activated catalyst systems, this method comprises: the catalyst compounds indicated in conjunction with activator and with following formula:

Wherein M is Hf, Zr or Ti；

Wherein n is 2；

37. the method for activated catalyst systems, this method comprises: the catalyst compounds indicated in conjunction with activator and with following formula:

Wherein M is Hf, Zr or Ti；

Wherein Y is selected from divalent C₃-C₂₀Alkyl, halogen, O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are suitable whole It counts to provide electroneutral part, and combinations thereof；With

38. according to the method for claim 37, [the O with fac-mer arrangement¹,N,S]-[N,S,O²]。

39. according to the method for claim 37, [the O with mer-fac arrangement¹,N,S]-[N,S,O²]。

40. according to the method for claim 37, [the O with fac-fac arrangement¹,N,S]-[N,S,O²]。

41. wherein the activation of catalyst compounds makes [O according to the method for any one of claim 36-40¹,N,S]-[N,S, O²] it is rearranged to fac-mer arrangement.

42. wherein the activation of catalyst compounds makes [O according to the method for any one of claim 36-40¹,N,S]-[N,S, O²] it is rearranged to mer-fac arrangement.

43. wherein the activation of catalyst compounds makes [O according to the method for any one of claim 36-40¹,N,S]-[N,S, O²] it is rearranged to fac-fac arrangement.

44. a kind of method of olefin polymerization, this method includes under polymerization conditions, contacting one or more alkene and according to right It is required that the catalyst system of any one of 24-28, produces polyolefin.

45. a kind of method of olefin polymerization, this method comprises:

Under polymerization conditions, one or more alkene and catalyst system are contacted, polyolefin is produced, which includes living Agent and the catalyst compounds indicated with following formula:

Wherein M is Hf, Zr or Ti；

Wherein n is 2；

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It independently is hydrogen, C₁-C₁₀Alkyl, C₁-C₁₀Alkyl, packet Containing halogen, O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_x Or PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are suitable integers to provide electroneutral part or two A or more R¹-R¹¹It can be independently connected together, form C₄-C₆₂Cricoid ring structure.

46. a kind of method of olefin polymerization, this method:

Wherein M is Hf, Zr or Ti；

47. a kind of method of olefin polymerization, this method comprises:

Wherein thio-salalen ligand is indicated with following formula:

Wherein metalating agent is indicated with following formula: MX¹X²X³X⁴

Wherein catalyst precarsor is indicated with following formula:

Wherein each solid line in the chemical formula represents covalent bond and each dotted line represents modified covalent degree and change The chemical bond of the coordination degree of change；

Wherein M is Hf, Zr or Ti；

Wherein every X¹, X², X³And X⁴It independently is monovalent C₁-C₂₀Alkyl, halogen, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR *_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_xOr PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x is Suitable integer is to provide electroneutral part；

48. according to the method for claim 46, [the O with fac-mer arrangement¹,N,S]-[N,S,O²]。

49. according to the method for claim 46, [the O with mer-fac arrangement¹,N,S]-[N,S,O²]。

50. according to the method for claim 46, [the O with fac-fac arrangement¹,N,S]-[N,S,O²]。

51. according to the method for claim 47, [the O with fac-mer arrangement¹,N,S]-[N,S,O²]。

52. according to the method for claim 47, [the O with mer-fac arrangement¹,N,S]-[N,S,O²]。

53. according to the method for claim 47, [the O with fac-fac arrangement¹,N,S]-[N,S,O²]。

54. wherein the activation of catalyst compounds makes [O according to the method for any one of claim 45-53¹,N,S]-[N,S, O²] it is rearranged to fac-mer arrangement.

55. wherein the activation of catalyst compounds makes [O according to the method for any one of claim 45-53¹,N,S]-[N,S, O²] it is rearranged to mer-fac arrangement.

56. wherein the activation of catalyst compounds makes [O according to the method for any one of claim 45-53¹,N,S]-[N,S, O²] it is rearranged to fac-fac arrangement.

57. according to the method for any one of claim 45-53, wherein polymerizing condition includes 0 DEG C -300 DEG C of temperature, The pressure of 0.35MPa-10MPa and -24 hours 0.1 minute time.

58. one or more of them alkene contains propylene according to the method for any one of claim 45-53.

59. wherein polyolefin has at least 50mol% propylene according to the method for any one of claim 45-53.

60. wherein polyolefin has at least 75mol% propylene according to the method for any one of claim 45-53.

61. wherein polyolefin has at least 85mol% propylene according to the method for any one of claim 45-53.

62. wherein polyolefin has the meso more than or equal to 90wt% according to the method for any one of claim 45-53 Isotaxy five unit group [mmmm] concentration, the total weight based on polymer.

63. wherein polyolefin has the meso more than or equal to 99wt% according to the method for any one of claim 45-53 Isotaxy five unit group [mmmm] concentration, the total weight based on polymer.

64. according to the method for any one of claim 45-53, wherein contacting thio-salalen before in conjunction with activator Ligand and metalating agent, and then in the case where no separating catalyst compound, in conjunction with activator.

65. according to the method for any one of claim 45-53, wherein in the presence of an activator, being deposited in one or more alkene Under, or a combination thereof under, contact thio-salalen ligand and metalating agent.

66. the method for preparing thio-salalen catalyst compounds, this method comprises:

Wherein M is Hf, Zr or Ti；

Wherein every R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹It independently is hydrogen, C₁-C₄₀Alkyl, C₁-C₄₀Alkyl, packet Containing halogen, O, S, Se, Te, NR*_x, OR*, SeR*, TeR*, PR*_x, AsR*_x, SbR*_x, SR*, BR*_x, SiR*_x, GeR*_x, SnR*_x Or PbR*_x, wherein each R* is independently C₁-C₂₀Alkyl and wherein x are suitable integers to provide electroneutral part or two A or more R¹-R¹¹It can be independently connected together, form C₄-C₆₂Cricoid ring structure.

67. the method for claim 66 further comprises making amineothiot NH₂- Y-SH, halogenated-methylphenol and salicylide are anti- It answers, forms thio-salalen ligand.

68. the method for claim 66, including make amineothiot NH₂- Y-SH is reacted with halogenated-methylphenol, forms amino-sulphur Generation-methylphenol, and make amino-it is thio-methylphenol and bigcatkin willow aldehyde reaction.

69. the method for claim 66, including make amineothiot NH₂- Y-SH and bigcatkin willow aldehyde reaction form mercaptan imino group phenol, With make halogenated-methylphenol and mercaptan imino group phenol reactant.

70. wherein salicylide is by R according to the method for any one of claim 66-69¹, R², R³, R⁴And R¹¹Replace.

71. according to the method for any one of claim 66-69, wherein halogenated-methylphenol is by R⁵, R⁶, R⁷, R⁸, R⁹And R¹⁰It takes Generation.

72. according to the method for any one of claim 66-69, wherein R⁴, R⁵Or combinations thereof be carbazyl.

73. according to the method for any one of claim 66-69, wherein R⁴, R⁵Or combinations thereof be 3,6- di-t-butyl carbazole -9- Base.